DE2024244C2 - Photosensitive condensation product containing diazonium groups and process for its preparation - Google Patents

Description

It is known that light-sensitive aromatic diazonium compounds are used for printing copier materials to be used for the production of single copies or printing plates.

One has in particular for the production of tanning images or planographic printing forms, in which the copy layer should be made insoluble or oleophilic by exposure to light, advantageously higher molecular weight diazonium salts with several dlazonium groups used in the molecule. These diazonium compounds mostly have resinous character and are z. B. by introducing dlazonium groups in phenol-formaldehyde condensate resins by means of conversion, reduction and dlazoteric or by other known reactions obtain. The diazo resins obtained thereafter, however, show certain disadvantages, e.g. B. a very limited one Shelf life, and have therefore not acquired any practical importance.

Another way of obtaining polyfunctional diazonium salts is by adding certain aromatic salts Diazonium salts in an acidic condensing agent with active carbonyl compounds, in particular Formaldehyde, has condensed. This type of higher molecular weight diazonium compounds is widely used Scale for the production of Koplermatertallen, especially for the production of Druc-Rformu, used.

Of these compounds, e.g. B. In DE-PS 5 96 731 and GB-PS 7 12 606 are described especially the condensation products of Dlphenylamlndlazonumalzen with formaldehyde great technical Gained importance.

The preparation of such and similar diazo resins is also in US-PS 26 79 498, 30 50 502 and the DE-PS 11 38 399, 11 38 400, 11 38 401, 11 42 871 and 11 54 123 described.

The production of tanning images by combining such diazo resins with hydrophilic colloids and optionally dyes or pigments In copier layers, among other things, in DE-PS 5 81 697, 8 32 546, 8 88 80S and the U.S. Patent No. 3,010,389.

By far the greatest importance, however, is this class of diazo resins for copier material for photomechanical purposes Obtained production of flat and offset printing forms. The diazo resins can be used in the copy layers as follows these materials without further additives or z. B. In combination with water-soluble colloids or with water-insoluble, light-sensitive polymers are used. As a carrier for such copying layers can e.g. B. waterproof paper with a suitable lithographic surface, superficially verselftes Cellulose acetate, metal carriers such as aluminum, zinc, copper, brass, chromium, niobium, tantalum, multi-metal carriers and lithographic stone can be used. Metals are preferred as substrates for long print runs. The most common is aluminum. The use of metal as a support for copy layers that Containing the diazo resins mentioned has, inter alia, the disadvantage that the adhesion of the peel-off products the diazo resins on the metallic supports are often not particularly good and, moreover, the metals the dlazo resin can have a corrosive effect.

A large number of proposals have been made to overcome these difficulties; B. the pretreatment of the metal surface with silicates (DE-PS 9 07147), with organic polyacids (DE-PS 10 91 433), with phosphonic acids and their derivatives (DE-PS 11 34 093), with Kalumhexafluorozlrkonat (US-PS 29 46 683), welter the use of diazo resins produced in phosphoric acid (BE-PS 6 08 789), the addition of phosphoric acid to the diazo resins and their use in a state free from metal salts (BE-PS 6 13 045, or the use of anodized aluminum surfaces.

The known diazo resins, although they are widely used in technology, still show a number other flaws. In this way, with the low molecular weight, advantageous in terms of shelf life Condensates on non-metallic carriers into which the preparation can easily sink, for example

on cellulose acetate film coated on the surface, only an unsatisfactory color acceptance of the exposure products.

Another shortcoming of the known Dlazo resins is that their commonly used double salt with zinc chloride and even more the metal salt-free phosphate or similar anions containing products > Provide copier layers that are highly sensitive to moisture and thus to fingerprints exhibit. Careless handling can easily damage the copy layer.

To overcome this disadvantage z. B. US Pat. No. 3,300,309 recommends converting the dlazo resins with certain phenolic coupling components to give addition products which are sparingly soluble in water and which result in less moisture-sensitive copying layers. These addition products, the salt or complex-type, relatively loose bonds _r however, are relatively easy, z. B. by organic solvents, and therefore do not have sufficient resistance under all conditions. Furthermore is particularly in the known Dlazo resins, which show an excellent thermostability, z. B. in the case of condensation products of S-alkoxy ^ -dlazodlphenylamlns with formaldehyde, the photosensitivity is not satisfactory.

There is also a general deficiency of the dlazo resins which have hitherto been preferred in the art in that this is usually difficult. B. as chlorides, sulfates or salts easier organic sulfonic acids, are separable and that their salts in organic solvents are often insufficient are soluble.

The object of the invention was to provide a light-sensitive condensation product of the initially specified To provide a genus that has a higher sensitivity to light and a lower sensitivity with good thermostability Moisture sensitivity in the unexposed state, which is easier in the metal-a '/ irelem state

deposit 158t and its properties are generally within wider limits than with known condensing

set station products as desired.

The object is achieved by means of a light-sensitive condensate product containing diazonium groups according to claim 1.

The condensation products according to the invention are opposite to the known, hitherto customary diazo resins a number of advantages.

Many of the dlazonium salt condensate products of the invention sink in certain carriers, e.g. B. In superficially saponified cellulose acetate, not as strongly as the well-known dlazo condensates. As a result, the exposure products that remain after development show better oleophilicity on their surface. Most of the new condensation products also have increased photosensitivity, lower moisture sensitivity, improved compatibility with polymers commonly used as layer additives and other advantages over corresponding known dlazonium salt condensate products or dlazo resins, as will be explained in detail in the following description.
3- ^s The light-sensitive condensation products are preferably in the dlazonium salt form. However, they can also be converted from this form in known catfish into light-sensitive azides, diazoamino compounds or diazosulfonates and used in this form.

The new condensation products can be prepared by adding at least one aromatic Dlazonium salt of one of the formulas given in claim 1, e.g. B. the general formula (R'-R ^J -} _p R ² -NjX,

w hereinafter referred to briefly as AN ₂ X, and at least one connection B, where the symbols the Im

Claim ι have given meaning, with at least one active carbonyl compound in free form

or condensed with agents that release such a carbonyl compound · η a strongly acidic medium.

Is as active Carbonylverblndung to prepare the condensation products of the invention virtually any compound, able to condense in a known catfish with compounds having reactive hydrogen atoms i> In a strongly acidic medium. Compounds which are suitable for this purpose are mentioned in DE-PS 5 96 731.

The by far preferred carbonyl compound is formaldehyde, as this is the most reactive and at the same time the cheapest Representative of this group of substances is. The other aliphatic or the aromatic and heterocyclic Aldehydes and even more so the ketones are much less reactive and can also often be undesirable Enter into side reactions under the condensation conditions. Formaldehyde should be used in this Description are understood: aqueous solutions of formaldehyde, gaseous formaldehyde, oligomers and polymers of formaldehyde, such as trioxane and paraformaldehyde, and other formaldehyde-releasing agents Medium, e.g. B. Urotropin.

Another process for the preparation of DlazonlumrrMscl.kondensaten of the above general "Type is described in DE-OS 20 24 242 in detail.

This process consists in using a modified Zweltkompor.ente B, the general formula

Ef-CHR ₀ -O-Rj) ,,,

uses what

E is a residue formed by splitting off m H-alomes from a compound B as defined above,
f> 5 R ₀ H, an aryl, alkyl or heterocyclic radical, preferably hydrogen.

R _{6 is} H, an alkyl or acyl radical with 1 to 4 carbon atoms or a phenyl radical and preferably hydrogen, methyl, ethyl or acetyl and

m is a positive integer from I to IO.

It can be assumed that when the condensation is carried out, component B ₁ reacts completely or partially with intermolecular splitting off of HOR ,, with the compound AN ₂ X or, if there is an excess of component B _1, also with itself to form condensation products.

The behavior and the composition of the reaction products speaks for such a course of the door Condensation. ·>

A large number of variants are possible with this process, which relate to the implementation of the condensation, the proportions used or the use of other additives, e.g. B. of active carbonyl compounds or components B.

The condensation according to the invention is carried out in the presence of a strongly acidic condensation agent. Preferred catfish are concentrated, moderately strong to strong acids, the acidity of which corresponds to io of diluent. The condensing agent should also be chosen so that it is under Condensation is liquid.

Acids suitable as condensing agents are, for example, in US Pat. No. 3,235,382, column 1, cell 71 to Column 2, cell S, called.

Particularly suitable Kondensatlonsmliiel are phosphoric acid, methanesulfonic acid and sulfuric acid in 15 concentrations of at least 40, preferably 70 to 100, weight - are used.%. The remainder is in general water, but can also be completely or partially composed of solvents ¹ , e.g. B. methanol, acetic acid and N-Methylpyrrolldon exist. Good results are obtained, for example, if 85% pure phosphoric acid, 80% pure sulfuric acid and 90% pure methanesulfonic acid are used.

85% lge phosphoric acid is a fairly mild condensing agent, in which the condensation is reduced to very 20 f-j gentle catfish can be carried out. It is therefore the most preferred condensing agent for everyone Combinations of compounds that react quickly enough under these rather mild conditions. 90% methanesulfonic acid is a stronger agent. This acid has the further great advantage that it is a Can solve a variety of components B and Bi.

If diazonium salts are used for the mixed condensation, which are in the form of the often used metal halides, If double salts are present, it is generally advisable to dissolve them in a condensate medium, then dry them Pass nitrogen or dry air through the mixture until all chloride ions are in gaseous form Hydrochloric acid has escaped, and then the halogen-VIfrele solution for the condensations too use.

The amount of acid used as the condensate can vary within wide limits. It is possible, for example W ι, 1 to 100 parts by weight per part by weight Telle acid-Tell the mixture of _AN; Use X + B + active carbonyl compound or from A-NjX + B ₁ , as the examples show. The amount of acid can also be greater without, however, deriving any major advantages from it. It is important to use enough condensing agent to produce an easily miscible reaction medium.

Depending on the condensation waste, the condensation partners and their concentration in the condensation medium, it may be necessary to accelerate the condensation reaction by heating or to slow it down by cooling. It is advisable not to choose a condensation temperature above 70 ° C, as the resistance of the diazo compounds AN ₂ X is limited at higher temperatures. However, it is possible to make many of the dlazocondensation products of the invention at a temperature above 70 ° C. The one for the

Production of the condensates preferred temperature range extends from +10 to + 50 ° C. «'

It is advantageous to work in a homogeneous reaction medium when carrying out all variants of mixed condensation, since this is the easiest way to achieve reproducible results. The components are therefore used, if they are not liquid, preferably in the form of solutions, the acids used as the condensation medium serving as the solvent, if at all possible. If individual compo-: but i th In the condensation media only sparingly soluble, they can also serve as fine suspension or as ■ "> go to the application .1 emulsion in the condensing agent. In any case, particularly good mechanical mixing of the condensation mixture must be ensured. ; _;

If inadequate solubility of the starting or end products complicates the condensation, it can also. ;: 5 ensured a homogeneous condensation medium through the use of organic solvents will. In each individual case, however, it must be checked which organic solvent is suitable 50 '· ,; Well suited for many cases. B. glacial acetic acid. Other solvents that can be used are e.g. B. Formic Acid, | 1

N-methylpyrrolldone and methanol. ^ When using organic solvents, however, it must be noted that the effectiveness g

of the customer's acid medium is reduced compared to the pure acid and that it is possible that the f:

Solvents can lead to side reactions. 55 f) The amount of active carbonyl compound, preferably formaldehyde, is equal to 1 mol of the sum of the η

molar amounts of the mixture of diazo compound AN ₂ X and component B is used (0.25 ?

Moles of AN ₂ X and 0.75 moles of B e.g. B. In this sense, 1 mole; an even more condensable chain consisting of:

already precondensed building blocks AN ₂ X or from already precondensed building blocks B becomes as 1 molecule: · ■;

understood), generally 0.5 to 4, preferably 0.65 to 2 mol. ⁶ O | l

From diazo compounds AN ₂ X and components B, which have one or two reactive positions II per molecule

contain, arise as a rule when using the carbonyl compound in the entire range given above _; fj

soluble condensation products. The use of soluble condensation products is ß for the erflndungsge- '

moderate copier materials preferred. ! Ί

Catfish one or both components AN ₂ X and B dre! or more condensable places, it may be favorable in some cases, especially under more energetic condensation conditions, with low

geren amounts of active carbonyl compound to work within the limits given above in order to obtain soluble j ';

Products to receive. ^ j

« Ti

For the preparation of the Mlschkondcnsaie the ratios c * 3r reactants AN ₂ X and B and the conditions of the condensation process can vary within wide limits.

In principle, it is possible to produce mixed condensates of any composition, i. H. all mixed condensates, in terms of their composition of a dlazo condensate, which is only a trace condensed in it

* Second component B contains up to a condensate of a second component B which only contains traces of a dlazo compound AN ₂ X condensed therein. Mixed condensates which contain, on average, 0.1 to 20 moles of the second component per mole of AN ₂ X, can in general be useful for the production of valuable photosensitive copier materials. Within this range, the mixed condensates normally have Εΐί, ι'-groups which differ significantly from those of the corresponding homocondensates.

If a mixed condensate contains, for example, 0.11 mol of component B per mol of AN ₂ X, which corresponds to 10 mol% of the condensate, this means by and large that in an ideal case each molecule of the condensate per unit of component B 9 units of AN ₂ X contains. In this case, a completely genuine mixed condensate can only be formed with a degree of condensation of at least 10. However, since the degree of condensation is often below 10 and, apart from in cases of a very high tendency to

^{| S} densatlon must expect the same units accumulate in individual molecules of the mixed condensate, it will often happen that are formed during the mixed condensation mixtures true mixed condensates with homocondensates that can not be easily separated in all cases. In the present description, the expression "mixed condensates" also includes mixtures of this type.

When a mixed condensate with a certain composition AN ₂ X: B = a: b is produced

- '• ^; soii, the starting materials can be carefully mixed in the ratio a: b and the mixture condensed, provided that the reactivity of the two compounds towards the active carbonyl compound is the same. However, since the reactivity of the individual components, for example with respect to formaldehyde, is usually different, it is generally advantageous. In each case, the ratio of the reactants and the condensation conditions which are necessary for the formation of a product of the desired composition can be determined by simple experiments. If the reactivity of component AN ₂ X with respect to the carbonyl compound differs significantly from that of component B, the condensation can be initiated with the component that is less easy to condense, and the other component can be added later.
In the simplest case, the co-condensation can be carried out. By using the component AN ₂ X

- '"and component B dissolves in an acid suitable as a condensing agent and either the carbonyl compound as such or in the form of a solution while stirring.

However, the implementation of the Mlschondensatlonsver method is not limited to the method just described. So it is possible in many cases. Mix components AN ₂ X and B with the carbon fiber compound and add the mixture or the individual components to the acid either in the form of a solution or

¹ ^ to be introduced as substances. On the other hand, it is also possible to dissolve the carbon monoxide compound in the acid and to introduce the two components one after the other or as a mixture in the form of the substances themselves or as a solution (s). Another possibility is that one of the components can be dissolved in the acid, and the other component and the coffee compound can be added either separately or in a mixture in the form of the substances themselves or in solution.

- "'The condensation reaction can be initiated with only one component and the second component, if necessary with an additional amount of carbon monoxide compound, to be added later. According to one of the methods It is even possible. Dlazo resins, e.g. B. those produced by acidic condensation of Dlphenylamln-4-dlazonlumsalzen with carbonyl compounds and have lower degrees of condensation, with a or to condense several components B and an active carbonyl group in an acidic medium. In

In some cases, a co-condensation of a low molecular weight homocondensate of a second component with AN ₂ X in the presence of a carbon monoxide compound in an acidic medium is possible, and even a molten condensation of homocondensates of a component AN ₂ X with homocondensates of a component B or mixed condensates of several components B in one acidic medium In the presence of carbon monoxide compounds can be carried out successfully.

By varying the condensation conditions given above, different end products can be obtained (Solubility and degree of incorporation of component B) even if the starting materials are the same Ratio can be used. It is therefore necessary to comply with uniform condensation conditions, if one has to repeat the production of a mixed condensate with uniform characteristics wishes.

If components B are used alone or with other substances for the production of the M ^ chkcr.dcnsate, then those components Bi are generally preferred for the production of soluble condensates in which m is 2 or a little greater than 2, for example 3 or 4. Within this group, components with / n = 2 are particularly preferred because they give condensation products with a simpler structure and, even when using several moles B, per mot AN ₂ X, the tendency to form gelled and possibly insoluble condensation products is reduced in many cases. This is of particular importance when using more vigorous condensation conditions. The components Bi in which m is greater than 2 are preferred in smaller

Amount used. In general, the amount of such compounds does not become 1 mole per mole of dlazo compound

exceed.

In order to determine the upper limit, however, the experiment must decide on a case-by-case basis. An important

The application of such components, in which m is greater than 2, entails using them combined with those with m = 2 for condensation.

It is also possible. Components Bi with / ?; = I to use for condensation, but you come when in the connection AN ₂ X /; = I is, to dlazocondensates, which have only one diazo cap per molecule

wear. The use of such condensate products in copings is generally not preferred. However, the combination of components B ₁ , in which m = I, with those which have an m of 2 or more can be advantageous. In these cases the first-mentioned component B (/ »= 1) can play the role of a» regulator «for the molecule size in the condensation.

In those cases in which In component Bi m is equal to or greater than 2 and component B, per mole of AN ₂ X, is used in an amount that _{contains less than 1 group equivalent of -CHR 0} OR _n groups (1 mole of component Bi with m = 2 contains, for example, 2 group equivalents), so it is advisable to add still active carbonyl compounds, preferably formaldehyde, at least enough that the sum of the group equivalents -CHR ₀ ORj and the molar amount of des multiplied by 2 added formaldehyde (the sifiü its condensation equivalents) is at least 1 equivalent per mole of dazo compound, in addition, further formaldehyde can be added, but the sum of the condensation equivalents explained above will generally rarely exceed 4. In special cases, however, more formaldehyde can be used. Another possibility to get higher molecular weight condensates when using component B, with m = 1, is to use still active carbonyl compounds, preferably formaldehyde, in the production of the condensates, even in cases where 1 per mole of dlazo compound is used Moles or more moles of component B may be used. In these cases, at least 0.5 mol of formaldehyde should be added per mole of component B, and per mole of dlazo compound which is more than component B,. However, the formaldehyde addition will seldom exceed an amount of 2 mol per mol of dlazo compound and component Bi.

The average molecular weights of the condensate products can vary depending on the Wan! the Kcndensailonsteüneh- v> mer and conditions are widely varied. However, it has been shown that mixed condensates with molecular weights between about 500 and 10,000 are preferably suitable for the production of good copier materials. It is of course to be noted that these are mostly mean values and that the molecular weights of the individual constituents of each condensate obtained are statistically distributed around this mean value. The type of distribution is shown in some examples using a fractionation of the condensates obtained.

The mixtures obtained by condensation can be used directly or further processed. Man can also work up the mixture and separate the condensates in solid form.

The condensation mixtures can be worked up in different ways. The method is that chemical and physical properties of the respective reaction product adapted. Mixed condensates, which contain a relatively large amount of the second component can often be obtained by stirring the condensate mixture be separated in water. In these cases it is often possible that a water-soluble mixed condensate Can be separated from the aqueous mother liquor in the form of any sparingly soluble salt. If the mixed condensate is water-soluble but sparingly soluble in organic solvents, it is often possible, the product by diluting the reaction mixture with an organic solvent, e.g. B. with a lower alcohol or a lower ketone.

An advantage of many of the condensates according to the invention is that they are in the form of salts, which of complex-forming metal salts are free, can be easily separated. For example, there are many condensates Sulphates, chlorides and bromides, which are sparingly soluble in water and from aqueous solutions of the condensation mixtures easily precipitated by adding the appropriate acids or their water-soluble salts can be.

The following groups of components AN ₂ X and / or B, which bring about the condensability, come into consideration within the scope of the definitions given in claims 1 to 5:

1. Aryl radicals and heterocyclic radicals which have core positions capable of condensation. Are preferred those residues in which these core positions are still activated. This activation can e.g. B. take place « by annealing with further aromatic rings or by substitution by groups such as -OH, -O-alkyl, -O-aryl, -SH, -S-alkyl, -S-aryl, -alkyl, -aryl, -amino, -alkylamino, -dlalkylamino, -Arylamlno and -Diarylamlno. In addition to these activating substances, the condensable aromatic or heterocyclic radicals and radicals which prevent condensation, e.g. B. Nitro or sulfonic acid groups occur if the activation brought about by other residues is only> ° is reduced but not canceled.

2. Residues which are themselves accessible to condensation and directly to iso- or heterocyclic radicals or to allphatic residues can be bound or which are optionally linked directly to one another. Belong here Groups such as carboxylic acid amide, sulfonic acid amide, N-alkylsulfonic acid amide, N-arylsulfonic acid amide, Nltrll-, urea, thiourea, urethane, ureldo-, thloureldo-, glyoxaldlureln-, imldazolon-, guanidine, Dicyandiamide and amino groups attached directly to aromatic rings.

_{To explain the components of the general formula AN 2} X, B and Bi to be used for the preparation of the diazo condensation products according to the invention, the compound types or individual compounds described below are cited in detail.

Diazonium compounds AN ₂ X

It is assumed that a the diazo group-bearing benzene nucleus, apart from a few exceptions, (z. B. 4-Dlazo-phenoI), the counters are not incorporated, is desaktlvleri so strong that a condensate ^ft 5 sation in compositions this ring is no longer possible under less energetic conditions.

The diazonium compounds to be used in the context of this invention therefore contain A in the radical in addition to the aromatic nucleus, which carries the diazo group, at least one aromatic ring

to

at least one condensable nuclear position and / or with substituents of the ones listed under 2 above Type, which are themselves capable of condensation.

When indicated in claim 1 for formula, the diazonium salts, which are used as starting material for the condensation products erflnciungsgemäßen Considering means ρ preferably 1. X can also be made • ^v of an acidic Substltuenten of the molecule. R ¹ preferably denotes an optionally substituted phenyl radical.

Substituents preferred are those which increase the reactivity of the core for the condensation; B. the groups alkyl, alkoxy, alkylmercapto, aryloxy, arylmercapto, hydroxy, mercapto, amines, anillno. R ^J Is a link between the rings R ¹ and R ^{3 of} the types specified in claim 1, in which the remainder R 'is always to be thought ^{on the left and the group R 2 on the right, if R 1 is} not symmetrical.

Examples of suitable D'azonlum connections are

2,3 ', 5-Trlmethoxy-dlphenyl-4-dlazonlumchlor! D

2,4 ', 5-Trlethoxy-dlphenyl-4-dlazonylumchIorld ¹⁵ • V [2- (3-methoxyphenyl) propylamine] -benzeneslazonum sulfate

4- [N-Ethyl-N- (4-methoxy-benzyl) -arnlno] -benzeneslazoniumchloride! D 4- [N- (Naphthyl- (2) -methyl) -N-n-propy'-amlno] -benzeneslazonium sulfate 4- [N- (3-Phenoxy-propyl) -N-methyl-amlno] -2,5-dlmethoxy-benzenedlazonlumtetrafluorobora ·

4- (N- (3-phenylmercapto-propyl) -N-ethyl-amlno] -2-chloro-5-methoxy-benzenedlazonlumchlorld ² " 4- [4- (3-methyl-phenoxy) -phenoxy] -2,5-dl-methoxy-benzenedlazonum sulfate

4- (4-methoxy-phenylmercapto) -2 S-dlalhoxy-benzoldlazonlumchlorld

Z.S-DlSthoxy ^ -phenoxy-benzoldlazonlumchlorld

4- (3,5-di-methoxy-benzoylamine) -2,5-di-ethoxy-benzene-lazonium-hexafluorophosphate

Dlphenylamine-4-dlazonlumsulfai

Particularly suitable mixed condensates are obtained when starting from diazonium compounds. In those

R ^{J is} a phenylene group which, in addition to the dlazonium group, can also carry one or two identical or different sub- ■ "'stluenten, u'le halogen atoms, alkyl groups with 1 to 4 carbon atoms or alkoxy

groups with I to 5 carbon atoms can be, and R ^{J is} a homeopolar bond or one of the members -O-, -S- or -NH-.

A particularly important group of diazonium compounds, which are preferred in the context of this invention

- ¹ S are used to produce the condensation products are the salts of Dlphenylamln-4-dlazonlumlons and its substitution products, since in many cases these are particularly easily accessible to condensation and the condensation products result in particularly valuable copying layers.

As substituents which are bound to the phenyl nuclei of the diphenylamine-4-dlazonium compounds are preferably alkyl groups with 1 to 3 and alkoxy groups with 1 to 5, especially those

■ »" with 1 to 2: carbon atoms, and the halogens are used. There are also no ^ .h the following groups -COOR (R = H, alkyl or aryl), -CONH ₂ , -CN, -COR (R = alkyl or Aryl), -SO ₂ OR (R = H, alkyl or aryl), NHCOR (R = alkyl or aryl), NHR and NRR '(R and R' = alkyl, aryl, aralkyl).

Examples of such substituents which are bonded to the phenyl nuclei of the diphenylamlndlazonum group can, are methyl, propyl, isobutyl, trlfluoromethyl, Methor.y, Dlfluormethoxy, ethoxy, Hydroxyä'iY.Dxy,

⁴ > ethoxyethoxy, fluorine, chlorine. Bromine, iodine, ethoxycarbonyl, phenoxycarbonyl, acetyl, methoxysulfonyl, ethoxysulfonyl, acetylamino, methylamlno, ethylamino, dimethylamine, dläthylamino, methyläthylamino, Phenylarr.lno, benzylamino, methylbenzylamino and ethylbenzylamino.

As Dlphenylamln-4-diazonium salts, for example, the diazonium salts come into question, which differ from the following Derive amines: 4-Amino-dlphenylamln, 4-Amino-3-melhoxy-dlphenylamln, 4-Amino-2-methoxy-

"> Diphenylamine, 4'-Amino-2-methoxy-dlphenyl-amln, 4'-Amino-4-methoxy-d! phenylamine, 4-Amino-3-methyldlphenylamine, 4-Amino-3-ethyl-dlphenylamine, 4 ' -Amlno-3-methyl-diphenyiamine, i'-Amlno ^ -methyl-dlphenylamine, 4-Amlno-3-ethoxy-dlphenylamln, 4-Am! No-3-hexyloxy-dlphenylamln, 4-Amlno-3 - /? - hydroxy-ethoxydiphenylamine, 4'-amino-2-methoxy-5-methyl-dlphenylamine, 4-amino-3-methoxy-6-methyl-dlphenylamine, V- amino-3,3'-dimethy5-diphenylamine, S'-ChloM -amino-dlphenylamine, 4'-amino-4-n-butoxy-diphenylamine, V- amino-S '^ - dlmethoxy-diphenylamine, 4-amino-diphenylamine-2-sulfonic acid, 4-amino-diphenylamine-2-carboxylic acid, 4-amino-dipheny-amine-2'-carboxylic acid, 4'-bromo-4-amine-diphenylamine.

Preference is given to 4-aminodiphenylamine and 3-methyl-4-aminodiphenylamine, particularly preferred the 3-alkoxy-4-amlno-dlphenylamine with 1 to 3 carbon atoms in the alkoxy group, in particular the 3-methoxy-4-amlno-dlphenylamine.

Diazonium compounds AN ₂ X for carrying out the condensation according to the invention can also be homocondensation products of the diazonium compounds mentioned with active carbonyl compounds. B. relatively low molecular weight representatives of the known dlazo resins, which according to the invention are to be regarded as welter condensable larger molecules with several diazonium groups.

The diazonium compounds AN ₂ X can be any soluble salt of a medium to strong acid

^{6: 1} are reacted, e.g. B. as the salt of sulfuric acid, orthophosphoric acid. Hydrochloric acid. Trifluoroacetic acid, methanesulfonic acid or benzenesulfonic acid. The sulfates and the phosphates are preferably used.

Components B

A large number of compounds for producing the mixed condensates are also used as components B into consideration. Substituted or unsubstituted aromatic hydrocarbons are an important class of the body and aromatic heterocyclic compounds, provided they have core positions which are in acidic Medium capable of reacting with active carbonyl compounds with condensation.

A large number of unsubstituted aromatic isocyclic and aromatic heterocyclic In this sense, compounds are suitable as components B, e.g. benzene (reacts poorly). Naphthalene, Anthracene, phenanthrene, pyrene, indene, fluorene, acenaphthene, thtaphene, furan, benzofuran, diphenylene oxide, Benzthlophen, Acridln, Carbazol and Phenothlazln.

Isocyclic and heterocyclic aromatics, especially those that are rather difficult to condense, can advantageously contain one or more identical or different substituents which activate the nucleus, thereby facilitating condensation and the solubility of both the components themselves and theirs Follow-up products are usually improved.

Examples of such substituents are:

-NR ⁷ R ¹ , -N (R ') ₂ , -OR ⁷ , -OR', - R ', - SR ⁷ and-SR ¹ ,

wherein R ^{7 is} H, -CO-alkyl, -CO-aryl, -CO-heteroyl, -CO-aralkyl, -SOi-alkyl, -SO ₂ -aryl, -SOi-aralkyl.

-SOi-Hetercyi, -CONHj, -CSNH ₁ , -CONH-Aiky !, -CQNH-Ary >>, -CQ-O-alkyl. -CO-Q-Ary !,

-CS-O-aryl, -CS-O-alkyl
and R * denotes hydrogen, an alkyl, aryl or aralkyl radical.

The following mean in detail:

Alkyl: branched or unbranched alkyl radical with 1 to 10 carbon atoms which can be substituted, e.g. B. by -halogen, -alkoxy, -OH, -COOH. -CONH ₂ , -CN, -CO-CH ,, -SO ₃ H, -PO ₃ H ₂ or neighboring hydrogens can be replaced by oxygen (epoxides) or removed (multiple bonds). The alkyl radical can also be interrupted, e.g. B. by -O-, -S-; -N (alkyl) -, -SOj-: -SO-;

Aryl: Mononuclear or polynuclear aromatic ring, including any alkyl, Alkoxy or aralkyl radicals containing 6 to 20 carbon atoms. The aryl nucleus can also have further substituents wear.

Aralkyl: A radical with 7 to 20 built up from alkyl and aryl radicals (according to the definition above) Carbon atoms.

Alkoxy: 0-alkyl radical, where alkyl has the meaning given above.

The radicals alkyl, aryl, aralkyl and alkoxy can be used one or more times, alone or next to one another occurrence. In order to keep the proportion of these substituents in the molecular weight of B in limits. Is in of the compound B the proportion of the four abovementioned and explained Substituienienypen in the structure of the Molecule limited, namely the primarily given aromatic iso- or heterocyclic ring or the condensed ring system to be substituted only to the extent that this aromatic on substitution

by alkyl groups only by a maximum of 10 carbon atoms

by aryl groups only by a maximum of 20 carbon atoms

by aralkyl groups. only by a maximum of 20 carbon atoms and by alkoxy groups only by a maximum of 10 carbon atoms

is enlarged. | .l

The total increase in carbon atoms due to these four types of substituents together (next to each other) |

should not exceed 30 carbon atoms on the primarily considered aromatic slam core.

From what has been said it follows that longer-chain substituents, ie those which contain a larger number of carbon atoms, can occur in fewer numbers next to one another than those with fewer carbon atoms. In general, the short-chain alkyl and alkoxy groups (1 to 4 carbon atoms) and the ti

smaller aromatic radicals in aryl and aralkyl groups preferred (up to 12 carbon atoms). there the egg

Corresponding compounds are better soluble in the condensation media and the condensation as a result |. '

which is easier to accomplish. For the same reason, the limitation of the substitution as &

welter detailed above. 55; '

In the iso- or heterocyclic condensable aromatic rings, the nuclei \

deactivating substituents, e.g. B. O ₂ N-, HOOC-, N = C-, HO ₃ S-, H ₂ O ₃ P-, Cl- and Br- occur, v!

as long as these do not cancel the condensability. This will especially be the case if the ring itself is already easily condensable or if it still has substituents that have a strong activating effect. Another possibility of introducing deactivating substituents without the condensation of the ^Wl ring being reduced too much, is to replace the substituents in rare chains, e.g. B. aliphatic side chains to accommodate. [

The core condensation desaktlvlerer.de substituents are also acceptable in those cases in which the reactivity of the condensable core can be dispensed with, because there are substituents on the core which the condensation can attack. Such substituents have already been listed above.> 5. Let us just refer again to the groups -CO-NHj, -SO ₃ NHi; -SOjNH-Alkyl pointed out.

The compounds to be used as components B or as components Bi derived from these can according to the above z. B. belong to the following groups of substances:

Aromatic (iso- and heterocyclic) unsubstituted aromatic amines
Phenols and thilophenols
Phenol ethers and aromatic thiols ⁵ aromatics, soft by alkyl, aralkyl or aryl radicals; are substituted

Urea, thiourea, carboxamides (aliphatic and aromatic) Sulfonic acid amides (aliphatic and aromatic).

Individual representatives will be listed later.

In the context of this invention, preference is given to using soluble representatives of the novel dlazo condensation products. In addition to an appropriate selection of components A-NvX and B or B ₁ according to their properties and their proportions, one also uses, in order to promote the formation of soluble condensation products, preferably components B and / or Bi, their molecular weight (amines are called free amines calculated, not in the sai form, acidic groups are calculated in the Η-form) less than 500,

!> preferably less than 250, is. If aromatic compounds are present, then, within these limits, those compounds are preferred which have no more than 4, preferably 1 to 2, especially 2, aromatic individual lengths (linked and / or linked via homopolar bonds and / or via intermediate links) *. Hold.

The use of compounds B or Bi of the lower molecular weight range is also favored because these are more easily soluble in the condensation medium and consequently easier to implement.

Of the listed classes of compounds from which the compounds B and Bi are recruited, those are generally preferred which cannot or can only be stored with difficulty under the acidic condensation conditions. The same applies to the diazo compounds AN ₂ X.

For this reason, compounds B and B are from the series of aromatic iso- and heterocycles

advantageous, which are unsubstituted or the radicals alkyl, aralkyl, aryl, alkoxy, alkylmercapto, Aryloxy, aryl mercapto, OH, SH and amino, possibly in addition to unself-lockable deactivating substituents,

z. B. COOH, carry. Of these, in turn, the aromatic isocycles and heterocycles are particularly preferred,

which are unsubstituted and / or as substituents the radicals alkyl, aralkyl, aryl, alkoxy, alkyl mercapto, Arylmercaplo-, Aryloxy- and ArylthSo- contain, especially when condensates

3 ° are desired which should not contain any salt-blending groups other than the dlazo group.

Selenium blends B or Bi, which differ from the Dlphenyläther and derived from Diphenylsulfld and one or two substituents, z. B. Halogen atoms, alkyl and alkoxy radicals, but are preferably unsubstituted.

If these compounds are condensed with Dlphenylamln-4-dlazonum salts, which are unsubstituted or substituted by a lower alkyl or alkoxy radical with up to 3 carbon atoms, mixed condensates are obtained, which can be easily and in good yield in the form of salts of hydrochloric acid, hydrobromic acid or suitable sulfonic acids given below can precipitate, especially when component B _{1 is used} in a ratio of 0.5 to 2 mol per mol of dlazo compound.

The condensation products according to the invention contain, per 1 mol of units of component AN ₂ X, generally on average 0.1 to 20 mol of units of components B and / or B ₁ . A particularly preferred range extends from 0.2 to 2 moles of B and / or B ₁ per mole of AN ₂ X.

The condensates can be used in very different ways. So can the novel Condensation productc In some cases in the form of the crude condensates, i. H. without separation of the condensing agent, can be applied. This is particularly possible if the amount of condensation

11th satlonsmlttel per mole of dlazo compound can be kept low.

In general, the new condensation products are deposited in the form of any salt and In this form after the addition of the desired further Schlchtbcstandtelle for the production of a copy material used.

The Dlazokondensatlonsprodukie can be deposited, for example, as salts of the following acids and can be used 5 ⁽⁾ :

Hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acids (pentavalent phosphorus), especially orthophosphoric acid, inorganic iso- and heteropoly acids, e.g. B. phosphotungstic acid, phosphotungstic acid, allphosphoric or aromatic phosphonic acids or their half esters, arsonic acids, phosphinic acids, trifluorosulfonic acid, amldosulfonic acid, selenic acid, hydrofluoric acid, hexafluorophosphoric acid., Perchloric acid, and also allphosphonic and aromatic sulfonic acids, for example. B. methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesltylenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosailzylic acid, naphthalene-1-sulfonic acid, naphthalen-2-sulfonic acid, 2,6-di-tert-butyl-naphthonic acid, 2,6-dichlorobenzene sulfonic acid -Dl-tert-butyl-naphthallndlsulphonic acid, 1,8-Dlnltronaphthalln-3,6-dlsulphonic acid, 4,4'-diazido-3,3'-dlsulphonic acid, 2-dlazo-1-naphthol-4-sulphonic acid, 2- Dlazo ^wl l-naphthoi-5-sulphonic acid and l-dlazo-2-naphthol-4-sulphonic acid. Further organic sulfonic acids which can be used for separating the condensates are given in Spatien 2 to 5 of US Pat. No. 3,219,447.

The new Dlazokondensatlonsprodukie can also in the form of the double salts with metal halides or -pseudohalogenlden, z. B. the metals zinc, cadmium. Cobalt, tin, and Elsen, deposited as reaction products with Natrlumtetraphenylborat or with 2-Nltro-lndandlon- (l, 3) and in a known catfish ⁶ ^ used

You can welter also by the action of sodium sulfate, sodium sulfate or amines in the appropriate Diazosulfonates. Azides or diazoamino compounds, are converted and in this form, as in known to the Dlazo resins.

IO

The technical advantages of using the new Dlazokondensallonsprodukte brings, the following were already approached above:

a) Less sinking of the Dlazo junction into carriers who are prone to this phenomenon, for example on superficially softened cellulose acetate film. The result is excellent oleophilic image- s pose after exposure.

b) Lower sensitivity of the copying layers to fingerprints.

Both advantages generally become more and more evident the more the number of built-in components increases. While in case a) the advantage is generally noticeable in the case of condensates which contain only 0.1 mol of B and / or B per mol of AN ₂ X, in case b) only about 0.5 mol is obtained In some cases, the desired effect is only achieved with a higher degree of installation of these components.

In addition to the above, there are other advantages when using the new condensate products. Compared to the known dlazo resins, an improved effective photosensitivity of the copier layers produced with the new condensate products is observed, ie one gets by with shorter exposure times when using the same light source. This effect also generally increases with an increasing content of B and / or Bi an and is of different sizes depending on the type of component B or B ₁ selected. The effect is generally more noticeable, the higher the molecular weight of component B or Bi. In general, the increase in the size of the components is effective by another aromatic ring stronger than an equal increase in molecular weight due to other residues.

As the content of a suitable second component B or B increases, the resinous character of the mixed condensates increases more and more pronounced, while the salt character with decreasing content of diazonium salt groups decreases in the condensate molecule. Consequently, the mixed condensates are more compatible with polymers that contain no isolable groups.

For the same reason, the mixed condensates often have good film-forming properties, and so do the films show improved flexibility and, in many cases, good stability in the exposed state against various caustic agents. So it is possible with a number of Mlschkondensaten without the usual one Addition of resins to produce copier layers with a satisfactory etch resistance, which can be used, for example, for the photomechanical production of intaglio printing forms and copied circuits.

For this purpose, the mixed condensates are particularly suitable that contain components with acidic or alkaline: caustic agents cannot form salt and have no tendency to hydrolytic cleavage, d. H. Secondary components from the range of aromatic hydrocarbons that are either unsubstituted or by Alkyl, alkoxy, alkyl mercapto, aryloxy or aryl mercapto groups are substituted.

A particularly favorable group of condensation products is derived from components B or Bi, which contain 2 benzene rings that are linked by a bridge member.

The mixed condensates from components B and especially B are particularly preferred in this series. the derive from diphenyl ether or diphenyl sulfide, with diphenylamine-4-dlazonium salts, in particular 3-alkoxydlphenylamine-4-dlazonium salts. These condensates have a high sensitivity to light, the condensates from 3-alkoxy-dlphenylamine-4-dlazonium salt at the same time a surprisingly good storage bar. The corresponding Condensate products, especially with components Bi, are particularly simple and under mild Conditions producible. Diphenyl ether derivatives of the Bi type, which are used for the production of condensate products Those eligible are commercially available.

In contrast to the well-known Dlazo resins, the new condensation products are in many cases very good easily by adding hydrochloric acid or saline solution in the form of chlorides or analogously as bromides aqueous solution separable. For this reason alone, the new types of condensation products are in the Can be used with advantage in cases where up to now the halides which can only be separated out in a complicated way known diazo resins found preferred application, such. B. for the production of screen printing forms. the In addition, chlorides can easily be converted into the salts of non-volatile acids, e.g. B. in the orthophosphates, transform, which of course also in a direct way, z. B. by condensation of the dlazonium phosphates in Phosphoric acid can be obtained.

A special group of the new condensate products shows with regard to the acid resistance of the Exposure products, e.g. B. to phosphoric acid-containing developer solutions, and their adhesion special advantages on metallic substrates. These are the condensation products, which are phosphonic acid groups wear.

The exposure products of these condensates adhere, for. B. well roughened only by metal brushes- >> ten aluminum foils without these having been provided with one of the well-known chemical Hafischlichen, even if the products are used in the form of the double salts.

Another special group of mixed condensates has particular advantages, particularly when it comes to hardening of hydrophilic colloids. These include mixed condensates made from diphenylamine-4-dlazonium salts and urea or similar connections. Kolloldschlehten, which hardened with these condensates under the influence of smell after hardening show a better hydropod than those made with the Dlazo resins known up to now Are senslllslert. This effect is important for the production of printing forms as they are, for. Am U.S. Patent No. 3,085,008.

It is also noteworthy that mixed condensates, consisting of dlazonium salts and an excess of phenols obtained, with aqueous-alkaline development (possibly with the addition of a little solvent) positive * 5 Able to deliver copies.

The new condensate products can be dissolved in Koplermaterlallen with In water and with In Combine water-insoluble polymers. Especially the production of copy layers, which are water-

Il

contain insoluble polymers, is simplified when using the novel condensation products, since the the latter particularly easily in the form of salts compatible with these polymers, which in a number of organic ones Solvents are very soluble can be obtained.

To produce the copy layer, the procedure is analogous to that of the known Dlazo resins, i.e. H. the dlazo condensates are dissolved individually or, if necessary, together with other Schlchtbestandtellen in one suitable solvent and coated the intended carrier with the solution thus obtained. Suitable Carriers are, for example, those mentioned in the introduction to the present description.

A large number of substances can be added to the copy layers as additional components *. as Examples called selenium:

ίο acids, e.g. B. phosphoric acids (especially those of Swertlgen phosphorus, preferably orthophosphoric acid), phosphonic acids, Sulfuric acid, hydrobromic acid, organic sulfonic acids, e.g. B. toluenesulfonic acid, methanesulfonic acid and naphtha! in-1,5-dlsulfonic acid.

Water-soluble polymers, e.g. B. polyvinyl alcohol, polyethylene oxide, partially with verselftes polyvinyl acetate an acetyl content up to awa 40%, polyacrylamide, polydlmethylacrylamide, polyvinylpyrrolidone, polyvinylmethylformamide, Polyvinylmethylacetamld and copolymers of the monomers making up these polymers among themselves.

Polymers which are sparingly soluble or insoluble in water, e.g. B. phenolic resins, epoxy resins, oil-modified alkyd resins, amine-formaldehyde resins such as urea and melamine resins, polyamides, polyurethanes, polyvinyl resins, polyacrylic and polymethacrylic esters, polyvinyl acetate, polyvinyl chloride, polyesters or polyethers.
Printing plates with considerably higher pressure pad is obtained from emulsions which d'r mixed condensates in combination with Polyvinylfo.-rnalharzer. contained, especially on grained aluminum.

Colored or uncolored pigments, dyes

^ Plasticizers

Wetting agents Sensitizers Indicators fatty acids

The copying layers produced using the novel dlazo condensation products provide In rages in all cases negative copies of the applied originals. When adding phenolic resins to the copying layers, especially in excess of the mixed condensate, is obtained with alkaline development however, positive copies of the original.

- ^1ς Depending on the layer composition, carrier material and processing, single copies, relief images, tanning images, printing forms for screen printing, letterpress, gravure and planographic printing, or copied circuits can be produced using the new diazo condensates.

To further explain the invention, a number of connection types and Eli-zel- ' 'compounds listed, which as components B or as components B derived therefrom, for • »o Production of the condensation products come into consideration.

The preparation of compounds of the general formula B ₁ is known and is described in detail in the literature. Some of the Bi-type compounds are commercially available.

In the list below of components B and Bi, a grouping has been made been. Group characteristic Is the substance that activates the condensation in each case. Naturally, is at ■ »5 occurrences of 2 or more unequal activating substituents make the classification into a certain one Group not without arbitrariness.

A number of unsubstituted aromatic isocycles and heterocycles are already used as components B. enumerated.

In some cases it is possible to also use flavorings that are substituted solely by deactivating substituents are to be used as component B or as a master connection for component B.

Examples of this can be found in the first group of the list below.

However, the compounds listed in the next groups are preferred, ie compounds B. which carry at least one activating substituent, as well as compounds of type B ₁ which carry activating or other than the -CHR ^ ORj groups no further substituents.

Only aromatics substituted by deactivating groups

2-chloro-naphthalln

Naphthalene-2-phosphonic acid ^{6 (1} anthracene ^ -carboxylic acid

Pyrene-4-sulfonic acid Anthracene-2-sulfonic acid amld 6-chloro-1-hydroxymethylnaphthalene

4,4'-Bls-aceioxymethyl-dlphenylsulr "on ' ¹ ^ 4,4'-Bls-methoxymethyl-benzophenone

4-chloro-hydroxymethylbenzene

12th

Aromatic amines and their acylation products Aniline; Benzanllld, Acetanllld, p-toluene sulfonic acid ald

3,5-Dlmethyl-anllln

2-methyl-anllln s

3-ethyl-anllln

N-methyl-anllln

3-methyl-N-ethyl-aniln

N, N-Dlmethyl-anllln

3-ChIor-anllln io

4-ethoxy-anllln

N-methanesulfonyl-3-ethoxy-anllln

3-Methoxy-anllln 3-Methoxy-N, N-dimethyl-anllln

3-EthyImercapto-anllln 15

2-methyl-N-benzyl-anl! Ln

Dlphenylamln

4-methyl-dlphenylamine 4-hexyioxy-diphenylamine

4-chloro-dlphenylamine 20

4-Amlno-dlphenylamln 3 ', 4'-Dlmethoxy-3-methyl-dlphenylamine, 4'-Bromo-2,5-dlethoxy-dlphenylamine 4-Nltro-diphenylamine

OiphenyIamln-4-suifonic acid:> Diphenylamine-4-sulfonic acid amld N-methyl-diphenylamine N-benzyl-dlphenylamine

4-methoxy-N-benzyl-anllln

m-phenylenediamine i <>

N, N'-di-butyryl-m-pheny lendlaml η

1 -Methyl-phenylenedlamine- (3,5) 4-Amino-dlphenyl 3-aminol-phenylmethane

1-amino-naphthalene 35

2-methylamino-naphthalene o-Äcctamino ^ -methoxy-naphihailn 2,6-Dlamino-naphthalln 2-Amino-anthracene

3-amino-pyrene 4o

3-Dlmethylamlno-pyrene 2-Anlllno-pyrldln 3-Amino-carbazole 3-Dlmethylamino-dlphenylene oxide

4-Amino-diphenyl ether 45

4-Amino-dlphenyl sulphide

Phenols, ie compounds in which the OH group is directly on an isocyclic or heterocyclic aromatic ring system, which can consist of one or more aromatic rings. These rings
can also carry any other substituents if it is ensured that at least one condensable position in the molecule is retained.

Examples of catfish are:

a) Phenols of the general formula

(R ') "HO-y-X

where R * stands for a monovalent radical and s for an integer from 0 to 4.

The following combinations of R 'and s are given as examples: 65

13th

20th R " 24 244 Isomers Alkyl (Ci to C.-,) ν Everyone Alkyl (C ₄ to C ₁₁₁ ) 1 to 4 Everyone Halogen (F, Cl, Br, I) I to 2 Everyone Aralkyl optionally substituted
(C ₇ to C ₂ n) I to 2 Everyone Aryl optionally substituted
(C ₆ to C _: .i) I to 2 Everyone Alkoxy and alkyl mercapto
(C ₁ to Ci) I to 2 Everyone Alkoxy, A Iky I never reap to and Arulkoxy.
KKf. substituted (Cj to Ci ,,) I to 3 Everyone Aryloxy, aryl mercapto,
optionally substituted (C ₍ . to C> n) I to 2 Everyone Alkylamino. Dialkylamino
(C, to C ₄ ) I to 2 Everyone Arylamino (C ₆ to Cm) I to 2 Everyone Aryl - SO ₃ -. (C ₆ to Cu) I to 2 preferably para
to the OH group SOjH, POiH ₂ , AsOiH ₂ , COOH, NO ₂
and the corresponding esters
and amides I. preferably para
to the OH group I.

Mentioned as a special representative selenium:

phenol

2-hydroxy-methylhenzo!

4-hydroxy-cyclohexyl benzene

4-hydroxy-tert-butylbenzene · «) 2-Hydroxy-1,4-danylbenzene

3-Hydroxy-4-isopn: ipyl-1-methyl-benzene 3-Hydroxy-1,2,4,54et: ramethyl-benzene 4-fluorophenol

3-iodine phenol
2,5-Dlchlorophenol 4-Hydroxydiphen, ylmeihan 4-Hydroxycumene 4-Hydroxydlphenj I.

4'-Hydroxy-2,4-methyl-dlphenyl 5 "4-hydroxy-diphen, tlmethane-4'-sulfonic acid

2-Hydroxy-1,4-dlmetho: <y-benzene 6-Hydroxy-1,3-d IHt'hoxybenzene 4'-Hydroxyphenyl (2nd, 4-dlmethoxy-benzyl) ether

4'-Hydroxy-2,4,6-tyroline-ethyl-diphenyl ether 5 4-HydroxylphenylHher

4'-Hydroxy-phenyl- [2,4-dibutoxy-naphthyI- (1)] - ether 3'-Hydroxy-4-meihy! -Dlphenyl sulphide 4-amino-phenol 3-benzoylamino-plieriol 4-BenzolsulfonyUirninoiphenol 2-Ethylamino-phsnol 3-DimethyIamlno- | 3henciI 4'-Hydroxy-phenj (1- (2-methyl-phenyl) -sulfone

Phenol-4-sulfonic {li; rre s ^ft phenol-4-carbonsäurs

Phenol-2-carboxylic acid Phenol ^ -carboxylic acid methyl ester Phenol-S-carbonsHurwIIJiihylamid

14th

4-hydroxy-acctophynone

4-hydroxy-benzophynone

4-hydroxy-zlmlsilurc

3-hydroxy-zlmtsüureamld

4-hydroxy-benzyldenacetophenone 5

b) Phenols in which the phenolic OH group is in a polynuclear aromatic system. Mentioned as representative selenium:

2-hydroxy-naphthalene

5-Hydroxy-2,6-dlmethyl-naphthalln io

4-Hydroxy-2-methoxy-naphthalene 4-Hydroxy-1-butoxy-naphthalene 2-methoxy-naphthalene-6-sulfonic acid amd 5,7-chloro-1-hydroxy-naphthalene

2-Hydroxy-naphthalene-6-sulfonic acid υ

2-Hydroxy-naphthalene-3-carboxylic acid ald

Naphthsulton

1-hydroxy-phenanthrene

- »II..J« 1

* -i i / uiuAjr-auiiuaicii

1-hydroxy-anthrachinone 20

4-hydroxy-pyrene

2,6-dlacetoxy-naphthalene

c) Polyhydric phenols, e.g. B.

1,3-hydroxybenzene 25

1,3-Dlbenzoyloxy-benzene

4,4'-Dlhydroxy-dlphenylmethane 2,2-Bls- (4-hydroxy-3-methyl-phenyl) -propane

Bls- (4-hydroxyphenyl) sulfone

4,4'-dihydroxy-benzophenone 30

4,4'-Dlhydroxy-3,3'-dlchloro-dlphenyl ether 1,5-hydroxy-naphthalene

Bi-type derivatives of phenols 35

E) Ie "Phenol alcohols" obtainable by formaldehyde addition from the above-mentioned phenols and their ethers and esters on the aliphatic OH group can be used for the preparation of the diazo compounds. Numerous phenolic alcohols are described in the literature. A compilation can be found e.g. B. In the monograph by Martin "The Chemistry of Phenolic Resins", John Wiley & Sons NY, w 1956. Further reference is made to "Die Makromolekulare Chemie, 44, Selten 44-45 (1961)". Likewise, phenol alcohols and their esters and ethers come into consideration, which were obtained in other ways, e.g. B. by halogen methylation or reduction of phenol aldehydes or phenol carboxylic acids or their esters.

In addition to the phenol alcohols and their above-mentioned derivatives, those produced by esterification of the phenolic OH group of these compounds obtainable by means of carboxylic acids or sulfonic acids 45 Find use.

In detail z. B. the following phenol alcohols or their derivatives are suitable:

2-hydroxy-hydroxymethylbenzene

6-Hydroxy-2,4-dlmethy 1-1,3,5-trisydroxymethyl-benzene ⁵⁰

ö-Acetoxy ^ -methyl-l ^ -bls-acetoxymethyl-benzene 5-chloro-2-hydroxy-1,3-bis-hydroxymethyl-benzene 5-tert-butyl-2-hydroxy-1,3-bls-methoxymethyl-benzene

S-Benzyl ^ -acetoxy-l ^ -bls-acetoxymethyl-benzene

5-phenoxy-2-hydroxy-1,3-bls-hydroxymethylbenzene ⁵⁵

S-methoxycarbonyl ^ -hydroxy-l.S-bis-hydroxymethyl-benzene S-cumyl-i-hydroxy-l ^ -bls-methoxymethyl-benzene S-methylmercapto ^ -hydroxy-l ^ -bls-hydroxymethyl-benzene

5-ethoxy-2-hydroxy-1,3-bls-methoxymethyl-benzene

5-fluoro-2-hydroxy-6-methyl-1,3-bis-hydroxymethyl-benzene ^ω

S ^ chloro ^ -hydroxyAo-dlmethyl-l ^ -bls-hydroxymethyl-benzene S-ChloM-hydroxy ^ -methyl-l ^ -bls-hydroxymethyl-benzene

3,5-di-bromo-2-hydroxy-hydroxymethylbenzene 2,2'-dihydroxy-glycyl ether

Dehydroxymethylhydroquinone 05

4-Hydroxy-3,5-bios-hydroxymethyl-dij> henylether 2 _f 2'-bis- (4-hydroxy-3,5-bis-hydroxy-methyl-phenyl) -propane

Bls- (4-hydroxy-5-methyl-3-hydroxymethyl-phenyl) -sulfone

15th

3,4-dihydroxy-hydrox; methylbenzene 2,3-Dlhydroxy-1,4-bls-hydroxymethyl-at> l ^ -Hydroxy-S-methoxy-hydroxymethylbenzene 2,2'-Dlhydroxy-3,3'-bls-hydroxymethy! -Diphenylmethane

Thiophenols

Hs It is possible to use the corresponding thiophenols instead of the phenols. The phenols, however, are the Far preferable to thlophenols, including: therefore, because the latter are much more expensive, to side rake-IO Tend to honing, and many representatives have an unpleasant odor. The same goes for the corresponding Type Bi compounds.

Ethers of phenols and thlophenols and aromatic hydrocarbons

15 Suitable are e.g. B. the alkyl, aralkyl and aryl ethers listed under "phenols" and "thiophenols" Links. Aromatic hydrocarbons are suitable for condensation when they are most aromatic Core are substituted by alkyl, aryl or aralkyl groups.

For this group of substances it should be noted that ether, thioether and alkyl groups make the nucleus less susceptible to condensation than phenolic OH or SH groups. consequently a Substl- - ¹ is "not possible lutlon this group of substances by desaktlvierende Substltuenten To the extent as with phenols.

Named as an individual representative of the substance group selenium: (Cf. also the previous groups, where ether, Thioether or alkyl groups occur alongside other activating substances.)

"Methoxybenzene

2-methoxy-1-methyl-benzene 2-ethoxy-1, 4-dlethyl-benzene 4-methoxymethylbenzene 2-methoxydlphenyl - '"1.3-Dlethoxy-benzene

4-Methoxy-zlmtsäure 3,5-Dlmethoxy-benzyldenacetophynone Resorclndlacetamide 1,4-di-methoxy-benzene 1,2,4-trlmethoxy-benzene 2-phenoxy-ethanol and its methyl ether phenoxyacetic acid Phenoxymethylphosphonic acid amide phenoxymethylphosphonic acid 4-methylphenoxymethylphosphonic acid 4-tert-butyl-phenoxymethylphosphonic acid 4-chloro-phenoxymethylphosphonic acid Phenyl glycidyl ether and its reaction products in the acidic condensation medium 4-methoxyphenyl 3- (4-methoxyphenyl) -dlphenyl

Diphenyl ether
3,2'-di-methyl-di-phenyl ether 3,3'-di-chloro-di-phenyl ether 4,4'-di-butoxy-di-phenyl-imethane ^{5 (1} 4,4'-di-methoxy-di-phenyl

4,4'-Dibutoxy-dlphenyl ether 2,4-Dlmethoxy-5-methyl-diphenyl ether 3-Bromo-4-enethoxy-dlphenyl ether. 2-Isopropyl-5-methyl-dlphenyl ether 4,4'-D! Methoxy-dlphenylmethane 3-phenyl-dlphenyl ether 4-chloro-dlphenyl ether Bls-dlphenylyl- (4,4 ') - üther Naphthyl-i 1) -phenyl ether Dl- [naphthyl- (l)] - ether 1,3-Dlphenoxy-benzene 2,2-Bls- [4-phenoxy-phenyl] -propane 1,2-Bls ^ phenoxy-ethane 1,2,3-Trls-phenoxy-propane i, 3-bis-phenoxy-propanoK2) 2-methoxy-naphthalene-6-sulfonic acid amd 2,6-di-methoxy-naphthalene-2-methoxy-naphthalene-6-sulfonic acid

16

1 -Methoxy-phenanthrene

4-nitro-diphenyl ether

2-ethoxy-anthracene

4- (2,3-dihydroxypropoxy) pyrene

8-MethoEy-chinoHn 5

• -Methoxy-naphthalln ^ -carbonsäureanUld

4,4'-Bls-ethyImercapto-dlphenylether

4,4'-dimethoxydilphenyl sulfide

4-phenoxy-dlphenyl sulfide

2,4'-Dlmethoxy-dlphenyl sulphide io

toluene

1,2-dimethyl-benzene

1,3-dimethyl-benzene

1,4-ethylbenzene

1,3,5-tert-methyl-benzene 15

1,2,4,5-tetramethyl 1-benzene

Pentamethyl benzene

1,3-Dtlsopropy! -Benzene

2,6-dimethyl-naphthaJln

2-tert-butyl-naphthalene 20

9,10-dimethyl-anthracene

1 -Methyl-7-isopropyl-phenanthrene

Diphenyl

Diphenylmethane

Dibenzyl 25

Stilbene

1-phenyl-naphthalene

Dinaphthyl- (1,1 ') methane

- 30

From phenol ethers, thiophenol ethers, aromatic hydrocarbons
and heterocyclic compounds derived compounds of the type Bi

The compounds of the Bi type of this group of substances are, for example, by halomethylation of the im

The basic structure described in the last section and the subsequent conversion of the halomethyl groups into 35

the groups -CH ₂ OH, -CHiO-alkyl or CHr-O-acyl are obtained. G

Numerous halomethyl compounds (which carry this group directly on the aromatic nucleus), which are known as jf Intermediate products for the preparation of compounds of the type discussed above are fk

known. p

To give compounds of the type Bi, which deduce from phenol ethers "comes to -w by ^alkylation: X

or aralkylation of the phenolic OH group of phenol alcohols. ff

Suitable representatives of these classes of compounds are z. E.g .:% < Benzyl alcohol ψ Dlbenzyiather 45 ||

1,3-Bls-hydroxy methyl-benzene äl |

1,4-Bls-methoxymethyl-benzene; 'lj!, S-Bls-acetoxymethyl-naphthalln
1,4-Bls-hydroxymethyl-naphthalene

1-Hydroxymethyl-naphthalln 50 ^ |

2-hydroxymethyl-naphthalln ψ

9,10-Bls-methoxymethyl-anthracene ψ

9-Hydroxymethyl-phenanthrene ^ I

2,5-Bls-methoxymethyl-thlophen ^

2-hydroxymethyl-furan 55 jj

Bls-methoxymethyl-dlphenylenoxld '»] Benzhydrol |

1,4-Bls- (a-hydroxybenzyl) benzene ";

3-methyl-hydroxymethylbenzoI, 5

2,5-dimethyl-hydroxymethylbenzene «> . *;

2-methyl-S-isopropyl-hydroxymethylbenzene. ■

4,6-dimethyl-1,3-bls-hydroxymethyl-benzene %

2,5-dimethyl-1,4-bls-hydroxymethyl-benzene '■ 2,4,6-trimethyl-1,3-bis-hydroxymethyl-benzene

2,4,6-Trlmethyl-1,3,5-trl-methoxymethyl-benzene 65
2,3,5,6-Tetramethyl-1,4-bls-acetoxymethyl-benzene
2,4,5,6-Tetramethyl-1,3-bios-ethoxymethyl-benzene
2-methyl-1,5-bls-acetoxymethyl-naphthalln

17th

2-ethyl-S, 10-b ls-m ethoxy methyl anthracene

2,4-Dilsopropyl-hydroxymethylbenzene 4,6-Diisopropyl-1,3-bls-hydroxymethylbenzene 4,6-DllsopΓopyl-1,3-bis-raethoxymethyl-benzene - 1,3-Bls- (3-hydroxymethyl-phenoxy) -propane

1,5-bis (4-hydroxymethyl-phenoxy) pentane !, S-dihydroxymethyl-S-methoxy-S-n-hexyl-benzene 1,3-Dlhydroxymethyl-2-ethoxy-5-ethyl-benzene !, S-dihydroxymethyl ^ -benzyloxy-S-methoxycarbonyl-benzoI M-dihydroxymethyW-methoxy-S-bromo-benzene lJ-Dihydroxymethyl ^ -methoxy-S-curnyl-benzene lJ-Dlhydroxymethyl ^ -ethoxy-S-methylmercapto-benzene !, S-dihydroxymethyl ^ -ethoxy-S-phenoxy-benzene 1,3-Dlhydroxymethyl-2 ^ -diethoxy-benzene 1, S-DihydroxymethyW-methoxy-S-benzyl-benzoI 2,6-Bls-hydroxymethyl-naphthalln

Bls-methoxymethyl-diphenylene sulfide Bis-methoxymethyl-dlmethyldlphenylene oxide

!, S-DlmethoxymethyW-niethoxy-S-fluoro-benzene 1,3-di-methoxy methyl ^ -athoxy-S-methoxy-benzene !, S-dimethoxymethyl-i-methoxy-S-phenyl-benzene

Bts- [2- (4-hydroxymethylphenoxy) ethyl] ether U.S. di-methoxymethyl ^ -ethoxy-S-bromobenzene

l ^ -Dlacetoxymethyl ^ -athoxy-S-tert.-butyl-benzoI 1, S-dlacetoxymethyW-rntthoxy-S-phenylmercaptobenzene !, S-dlacetoxymethylU-methoxy-S-chloro-benzoI !, S-dlacetoxymethyl ^^ - dlmethoxy-benzoI 1,3-bis (2-methyl-4-benzyI-6-hydroxymethyI-phenoxy) propane

3,4-di-methoxy-hydroxymethylbenzene ^x o-bromoO ^ -dlmethoxy-hydroxymethylbenzene

4,5-dimethoxy-2-methyl-hydroxymethylbenzoI 2,3-di-methoxy-hydroxymethylbenzene 2,2'-Dlmethoxy-3,3'-bls-hydroxymethyl-5,5'-dlmethyIdlphenylmethan dihydroxymethyl-hydrochloride / methyl ether 4-methoxy-3,5-bls-hydroxymethyl-diphenyl ether

Bis- {4-ethoxy-5-methyl-3-hydroxymethyl-phenyl) sulfone

4-methoxymethyl-diphenyl ether 2-hydroxymethyl-diphenyl ether

4,4'-bis-hydroxymethyl-diphenyl ether <o 4,4'-bios-acetoxymethyl-diphenyl ether

4,4'-Bls-methoxymethyl-dlphenyl ether 4,4'-Bls-ethoxymethyl-dlphenyl ether 2,4'-Bls-methoxymethyl-dlphenyl ether

2,4,4'-Trls-methoxymethyl-dlphenyiather * s 2,4,2'-Trls-methoxymethyl-dlphenyl ether

2,4,2 ', 4'-Tetrakls-methoxymethyl-dlphenyl ether

Bls-methoxymethyM ^ '- dlmethyl-dlphenylether Bls-methoxymethyl ^^ -dlmethoxy-S-methyl-dlphenylather

Bis-methoxymethyl OJ'-dlmethyl-dlphenyl sulfide Bls-methoxymethyl-2,4'-dlmethoxy-dlphenyl sulfide 2,2'-dimethyl-4,4'-bs-hydroxymethyl-dlphenyl ether 4-chloro-4'-methoxymethyl-diphenyl ether 1,3-Bls- (4-methoxymethyl-phenoxy) -benzene 1,3-Bls- (4-methoxymethyl-phenoxy) -propane 4,4'-Bls-acetoxymethyl-dlphenylmethane 4,4'-Bls-methoxymethyl-diphenyl 4,4'-Bls-methoxymethyl-diphenyl sulfide δ-methylmercapto-S-methyl-hydroxymethylbenzene 2,2-bis- [4- <4-methoxymethyl-phenoxy) -phenyl] -propane 4,4'-Bls-phenoxymethyl-dlphenyl ether

Bls-methoxymethyl-4-phenoxydlphenylsuiride Bls-methoxymethyl-2-isopropyl-S-methyl-dlphenyl ether

Bls-methoxymethyl-S-bromo ^ -methoxy-dlphenyl ether Bls-methoxymethyl-4-ntro-dlphenyiather

The compounds of type B listed up to now are condensable by at least one in an acidic medium; Core position characterized in an aromatic ring.
The following organic acid camldc of type B are also condensable if they do not contain any aromatic

18th

table rings or those which no longer contain any condensable nuclear poslllons or which are very severely deactivated due to their substitution. This group of compounds contains at least one substance which is able to react with an active carbonyl compound with condensation. Examples of such substances are: -NH-CO-NH ₂ , -NH-CS-NH ₂ , -CO-NH ₁ , -CO-NH-alkyl, -SO ₂ -NH ₂ , -SOi-NH-CO-NH ₂ , -SOj-NH-alkyl and -NH-CO-NH-alkyl. 5

These substances can of course also be attached to aromatic nuclei, which themselves are replaced by corresponding Substitution are capable of condensation. Then both in the core and in the first mentioned Substituents condensation occur.

Selenium mentioned as examples for this general group of substances: ι ο

urea

Thiourea Ethylene urea N, N'-dimethylurea 15 Glyoxaldlurein

Oxamide

Amber acid diamond Adipic acid diamond Adipinic acid monoamld: o SebazInsSuredlamid Iminodiacetic acid lamld Dl-n-propylether-SJ'-dlcarboxylic acid lamld Cltronensäuretrlamld

Benzamide 25

Terephthalic acid diamond Isophthalic acid lamld Benzenesulfonic acid amide

m-Benzoldlsulfonsäuredlamld

p-Toluenesulfonic acid amd 30

2,6-DI-tert-butyl-naphthalln-1,5-dlsulfonic acid lamld

Adipic acid dinitrile

p-Toluene sulfonic acid-N-ethylamine 2,4,6-Trimethylbenzenesui: .msäureamld

Tetrahydronaphthalene sulfonic acid amide 35 Tetrahydronaphthallnsulfonsäuremethylamld (SO ₂ group in the hydrogenated ring)

3-Nltro-benzenesulphonic acid amId 4-methoxybenzenesulfonic acid amide

Benzene-1-sulfonic acid amd-S-carboxamide Benzene Trlsulfonsäuretrlamld 40 Phenol-2,4-dlsulfonsauredIamld

p-Amlnobenzenesulfonsäureamld

Melamine (as well as the lower amides of cyanuric acid) Benzoguanamines

Those of the Bi type can also be derived and used from compounds B of this type. Selenium mentioned as examples:

Bis-hydroxymethyl-urea Bls-hydroxymethyl-ethylene urea 50 Bls-hydroxymethyl-oxamld Bis-hydroxymethyl-succinic acid lamld Bls-methoxymethyl-adlpinsäuredlamid Bls-hydroxymelhyl-sebacic acid lamld Hydroxymethylbenzamide 55 Bls-hydroxymethyl-terephthalic acid lamld Hydroxymethylbenzenesulfonic acid amld Tetra (hydroxymethyl) melamine Hexa- (methoxymethyl) melamine

MH of the above list are the most important groups of substances, which are considered as components B or Bi in question come, been touched. But this does not exhaust the possibilities. B. also cyanuric acid hydrazides, Guanidine derivatives and aminopyrimidines can be used as components B.

The following examples describe the production of copier materials according to the invention Use of light-sensitive mixed condensates. 65

For more detailed identification of the mixed condensates used, is next to the result of the elemental analysis Still given in many examples. In what molar ratio - this is calculated from these analysis values - Dlazo connection, component B and / or B, are involved in the construction of the product. This

19th

The ratio was calculated using somewhat simplifying assumptions. These assumptions cannot and should not be Make statements about the exact structure of the mixed condensates according to the invention. However, they are enough ays to identify condensation products that are reproducible in terms of their properties.

As already mentioned above, in many cases the conditions of condensation, in particular also the proportions used, which are important or even necessary. The examples contain all information required for the production of the mixed condensates.

In the examples, weight points (parts by weight) and volume parts (parts by weight) are in the ratio of g to ml. Unless otherwise stated, percentages are percentages by weight and temperatures are given in ° C. at the analytical values mean N the total nitrogen content and ND the diazo nitrogen.

In general, no particular value was placed on complete drying of the condensation products. so that the products can still contain small amounts of water or condensation agent. aside from that In some cases, varying amounts of metal salts can be entrained during the deposition. It however, it is easily possible to determine the active substance content of the products from the analytical values recognize.

In the examples, the term “raw condensate” generally refers to the raw condensation obtained during the condensation Denotes condensation mixture, which normally also includes the condensation medium and possibly solvent contains.

For the sake of clarity, Table 1 below lists the diazo compounds AN ₂ X, components B and Bi under numbering, which are used to produce the mixed condensates contained in the copying material according to the invention. Reference is made to the numbering in the df. · .- examples

'UIIlICII *

Diazo 1: Diazo 2: Diazo 3: Diazo 4: Diazo 5: Diazo 6: Diazo 7: Diazo 8th: Diazo 9: Diazo 10: Diazo 11: Diazo 12: Diazo 13: Diazo 14:

Table Dlazo connection'm

Diphenylamine-4-dlazonum salt

3-methoxy-diphenylamine-4-dfazonum salt, 4'-methoxy-diphenylamine-4-dlazonum salt 2'-carboxy-dipheny-amin-4-dlazonium salt 2,4 ', 5-Trlethoxy-dlphenyl-4-dia7.onum salt 4- (4-methyl-phenylmercapto) -2,5-dimethoxy-benzoid / azonium salt 2,5-Dlmethoxy-4-phenoxy-benzenedlazonum salt 4- (2,5-Dlethoxy-benzoylamino) -2,5-dl9thoxy-benzenedlazonum salt 3-Meihoxy-diphenylenoxld-2-dlazonium salt 2-sulfo-4-dlazo-dlphenylamine (inner salt) 4 - [(N-methyl-N-naphthyl- (l) -methy!) AmlnoJ-benzenedlazonium salt 4-dlazo-dlphenylamine-3-carboxylic acid (inner salt) 2,5-Dimethoxy-4 - [(N-methyl-N-phenyimercaptoacetyl) aminol-benzenediazonium salt 4- [N-methyl-N - (/? - phenylmercaptoethyl) -arninol-benzene lazonium salt

Components B and

Number 1: 3,5-Dlmethyl-anllln No. 2 Diphenylamine No. 3: 4-chloro-diphenylamine No. 4: 3-methoxy-dlphenylamine No. 5: 4-methyl-phenylamine No. 6: 4-nitro-diphenylamine No. 7: 2-Dlmeihylamlno-naphthalln No. 8: phenol No. 9: 4-tert-butyl-phenol No. 10: 4-nitrophenol No. 11: 4-hydroxy-cylmamic acid No. 12: 4-hydroxybenzoic acid No. 13: 2-Hydroxy-naphthalene-6-sulphonic acid No. 14 benzene No. 15: Phanthrene No. 16: Mesltylen No. 17: Anisole No. 18: 2-phenoxy-ethanol No. 19: Phenoxyacetic acid No. 20: 3-methyl-phenoxymethyl-phosphonic acid No. 21: 4-chloro-phenoxymethyl-phosphonic acid No. 22: 4-lcrt.-Butyl-phcnoxymclhyl-ph () sphons! Luic No. 23: 2-Mülhoxy-naphthiilln-6-.stilfons! Lurc No. 24: Phonylcnoxld

20th

No. 25: p-toluenesulonsUurcamld No. 26: Ν, Ν'-Dlmethylol-bernstelnsauredlamld No. 27: sebacic acid lamld No. 28: Hexamethoxymethyl-melamln No. 29: N.N'-Dlmethylol-urstofT j No. 30: Ν, Ν'-Dlmethylol-ierephthalsäuredlamld No. 31: 2,6-Di-methyl-4-methyl-phenol No. 32: 2,6-dimethylol-4-methyl-anlsol No. 33: Dihydroxymethyl-durol No. 34: Dlacctoxymethyl-durol io No. 35: 1,3-Dlmethyl-4,6-dlmethylol-benzene No. 36: l ^ -DllsopropyM.o-dlmethylol-benzene No. 37: 1.S-dlacetoxymethyl-naphthalln No. 38: 1,4-dimethylol-benzene No. 39: Technical Bls-methoxymethyl-diphenyl ether (composition see. Example 21) is No. 40: 4,4'-dlacetoxymethyl-dlphenyl ether No. 41: 4,4'-Dlmethoxymetnyl-Dlphenyläther No. 42: 2,5-Diathoxymethyl-thlophen No. 43: 9, iö-Dimethoxymethy'i-anthracene No. 44: Benzhydrol 20 No. 45: 1,4-BMa-hydroxybenzyD-benzene No. 46: l ^ -DllsoproDyM.o-dlmelhoxymethyl-benzene No. 47: 4,4'-Dlmethoxymethyl-dlphenyl sulfide No. 48: methoxymethyl-diphenyl ether, obtained by Renlkilon from technical

chloromethyl diphenyl ether with sodium hypohydrate. 25th

(Composition see example 64)

No. 49: 2,2'-Bls- (4-hydroxymethyl-phenoxy) -dläthylaiher No. 50: 1,3-Bls- (4-hydroxymcthy I-phenoxy) propane No. 51: Bls-methxymethyl-dlphenylenoxide No. 52: 4,4'-Bls-methoxymethyl-dlphenylmethane "Λ No. 53: methoxymethylated phenyl No. 54: methoxymethylated 4,4'-dlmethyl-dlphenyl ether No. 55: methoxymethyl tert-2-isopropyl-5-methyl-dlphen; flather No. 56: methoxymethyl tert 3-bromo-4-methoxy-dlphenyl ether No. 57: methoxymethylated di-benzo-thlophen JS No. 58: methoxymethylated 1,4-di-phenoxybenzene Nf. 59: 2,6-bis (mclnOXymcihy'i) -4-niclnyi-pncnöl No. 60: diphenyl ether No. 61: N, N'-Dimethylol-oxamld No. 62: Adlplnsäuredlamld 40 No. 63: Ν, Ν'-Dlmethylol-adlplnsäuredlamld No. 64: Trimethyloltramld No. 65: p-Toluenesulfonic acid anil No. 66: p-Toluolsulfonsaureäthylamld No. 67: 1,3-Benzol-dlsulfonsauredlamld 45 No. 68: Phenylthlourea No. 69: phenylurea No. 70: 2-Benzoylamino-1,4-dlethoxy-benzene No. 71: 3-aminopyrene No. 72: 2-PhenyIamlnopyrldln 50 No. 73: Thlophen Examples I to

The following examples demonstrate the good to excellent oleophilicity of the exposure products from 35 der
novel condensation products on superficially softened cellulose acetate cases compared to the pure formaldehyde condensates of the diazo compounds with increased sensitivity to light at the same time. The composition of the condensation products and the coating solutions used are shown in Table 2. 60

21

Table 2

Example mixed condensate (MK)

Diazo compound
Λ - NjX component
B or B ₁ 1 Diazo 2, cf. 6th 2 Diazo 2, H ₂ PO / 5 or
5 + 2 3 Diazo 2, H ₂ PO ₄ " 5 4th Diazo 2, cf. 8th 5 Diazo 1, cf. 8th 6th Diazo 1, cf. 11th 7th Diazo 1, HSO ₄ " 10

Diazo I, HSO ₄

Diazo 1, HSO4 "

Diazo 1, HSO ₄ "

Diazo 2, HSO ₄ "Diazo 1, Cf

Diazo 2, HSO ₄ "Diazo 3, HSO ₄ "

CH ₂ O deposited as

14 + 15 -

16

17th

18 19

27

- ZnCl ₁

Cl

H ₂ PO ₄ "· H ₃ PO ₄

H ₂ PO ₄ "H ₃ PO ₄ raw condensate

Raw condensate

CH ₃ SO ₃ "HSO ₄ "

Cf

Cl

- ZnCl;

30th

- ZnCl ₂ 2

H ₂ PO ₄ "H ₃ PO ₄ CH ₃ SO ₃ "

Cf Cl

- ZnCl ₂

Ratio A - N ₂ X
to B or B ₁
in MK approx. Deletion
% MK Further
additions 1: 0.5 2% - 1: 0.75 2% - 1: 0.42 2% - 1: 0.15 to
1: 0.25 1%
Raw condensate - 1: 0.3 1%
Raw condensate - 1: 1.1 1.8% - 1: 0.8 2%

Additional salary of
9.6 C atoms
per N ₂ group

0.9%

2%

1: 0.5 1.2 1: 1 2.0 1: 1.46 2.0 1: 0.65 1.6 C: N = 23.6: 5 1.2

Solvent (parts by volume)

H ₂ O

HiO / n-butanol 96: 4

H ₂ OH ₂ O

H ₂ O

H ₂ O

ÄGMMÄ / DMF / H ₂ O

55: 35:

insoluble components filtered off

H ₂ O / ethanol 8: 2

H ₂ O

H ₂ OH ₂ O

H ₂ O

ÄGMMÄ / DMF / H ₂ O

55: 37:

continuation Ul 22nd Diazo compound component 31 CH ₂ O deposited as Ratio A - N-X Brush solution Further solvent O Example mixed condensate (MK) 23 AN ₂ X B or B ₁ to B or Bi % MK additions (Vol-jpmile) 24 33 in MK approx. 25th Diazo 2, H ₂ PO ₄ " 32 H ₂ PO ₄ "· H ₃ PO ₄ 1: 1 H ₂ O / C ₂ H <OH SJ - 35 + 37 1.65 8: 2 15th Diazo 2, HSO ₄ " Cl " 1: 1.1 - ÄGMMÄ Diazo 2, HSO ₄ " Cf 1: 1.1 1.0 - H ₂ O 16 Diazo 1, HSO ₄ " 36 Cf Extra salary 1.0 - H ₂ O 17th 34 of 9.6 carbon atoms 0.8 18th 26th 39 per N ₂ group Diazo 2, HSO ₄ " Cf 1: 2.4 - ÄGMMÄ Diazo 4, H ₂ PO ₄ " Cf 1: 1.1 1.65 - ÄGMMÄ 19th Diazo 2, HSO ₄ " 45 Cf Extra salary 1.0 - H ₂ O 20th 44 of 10.6 carbon atoms 1.0 21 39 per N ₂ group Diazo 1, HSO ₄ " 36 Cf 1: 0.716 - ÄGMMÄ Diazo 1, HSO ₄ " + Cf 1: 0.9 0.92 - ÄGMMÄ Diazo 2, HSO ₄ " + Raw condensate 1: 0.2 0.5 - H ₂ O Diazo 2, HSO ₄ " Cl " 1: 1.05 2.0 2 molecules H ₂ O a) 0.1 H, PO, / Diazo group '/ 2 molecule HjO b) 0.1 ZnCl: / Diazo group Diazo 1, HSO ₄ " - ZnCl, HjO + Cl · ₂ 0.1

Continuation

Example mixed condensate (MK)

Dowel connection Λ - N-X

Component B or B ₁

CH _; O Separated as

N.X Dispute resolution far Ratio A - % MK additions to B or Bi in MK approx.

Solvent (parts by volume)

27 Diazo 1, H ₂ PO ₄ _

+ Diazo 2, H ₂ PO ₄

- ZnCl

- ZnCl.

ZnCI; 2

ZnCl

Diazo 7th Cl Diazo 7, Cl

Diazo 8th Cf Diazo 9th Cl "

Diazo 2, HSO ₄ "Diazo 2, Cl" Diazo 6, Cf · - ^ γ ² Diazo 2, HSaf

25th

42

46 46

38 38

41 38 41

H ₂ PO ₄ H ₁ PO / nCI; Cf 2 Cf ZnCIj Cf 2 Cf ZnCI; Cf 2 Cl " ZnCI, Cf 2 Cl " ZnCI, 2

1.2

2.0

2.0
OI
2.0

1.0

1: 0.68 2.0 or 0.1 1: 5.4 1.0 or 0.1 1: 0.7 1.0 Extra salary
of 17 carbon atoms
per N2 group 1.0

H ₂ O

H ₂ O

H ₂ OH ₂ O

H _: O

H ₂ O

H ₂ OH ₂ O

H ₂ OH ₂ O

ÄGMMÄ = Ethyleneglykolmonomethylüiher DMF = Dimethylformamide

In the case of the purely aqueous brush solutions, the coating can be carried out by tamponing, in the case of the predominantly organic solvent-containing solutions with a knife gate valve. Warm air is used for drying. After imagewise exposure through a negative is developed .. example by wiping with water or the known buffered solutions of water-soluble coupling components?; z. B. those from the pyrazolone series. Then it is colored with bold paint, whereby the finishing products take on color. In a range of colors, it is also possible to enhance the image with varnishes, e.g. B. by the usual emulsion paints. The oleophilicity of the exposure products of the novel dlazo condensates is in all cases better than that of the formaldehyde condensates of the corresponding diazo compounds customary up to now.

This fact becomes clear through the following comparisons.

Formaldehyde condensate »of the diazo compounds 1 and 2, prepared in phosphoric acid according to Example 1 of DE-PS 1138 399 and Example 1 of DE-PS 1138401, provide with the coating described above and Processing only poor or no ink acceptance of the exposure products.

Addition of phosphoric acid to the coating solution worsens the result even further.

The novel condensation products produced in phosphoric acid, e.g. B. that of Examples 2, 3, 11, 15 to 17, 19, 21, 23, 27, 32, 33, 35, on the other hand, show good to excellent color acceptance in the image areas. These Oleophilicity is also not lost if phosphoric acid is added to the coating solutions. Be like that beisptelswe <s », for the coating solutions of Examples 8 and 16 to 22, 2 molecules of phosphoric acid for each diazo group added without reducing the color of the finishing products noticeably. In In Example 35, even 10 molecules of phosphoric acid are present per diazo group. Point in the same direction also Examples 4, 5 and 24, according to which crude condensates are dissolved in phosphoric acid without separation of the condensate substance for coating use.

These examples also demonstrate that even the incorporation of small amounts of component B or Bi sufficient to let the proper effect be merLÜch. This is e.g. B. with incorporation of 0.15 mol B per mole of diazo compound is already the case, even if these results are not yet optimal.

The progressiveness of the new condensation products compared to those made in sulfuric acid Formaldehyde condensates, deposited as zinc chloride double salt, which z. Z. preferably used as a diazo resin are shown in Examples 25, 29 and 33. Thus, with Ö, Li >> igen solutions of the new mixed condensate (Example 25) still brightly colored even after adding 2 molecules of phosphoric acid per diazo group Obtain printing forms from which prints can be made on the usual offset presses. With the 0.1% solution of the corresponding formaldehyde condensate (Example 26), on the other hand, is processed in the same way no significant ink acceptance achieved. Fairly sufficient ink acceptance is only achieved if the concentration of this diazo compound is increased several times.

The preparation and composition of the mixed condensates used in Examples 1 to 35 are described Described individually below.

example 1

In 16 Vt. Methanesulfonic acid (90% lg) are 10.8 pbw. 3-methoxy-dlphenylamine-4-dlazon! Umchlorid (97% lg) (Diazo 2, chloride, table 1). You wear 1.8 Gt. Paraformaldehyde and condensed for 10 minutes, being the temperature is kept below 30 ° C. Without delay, a prepared solution of 4.3 pbw is produced at 25 ° C. -to 4-Nltro-dlphenylamine (component B, no. 6, table 1) in 32 parts. 90% methanesulfonic acid with stirring added dropwise and stirred for a further 1/1 hour. Without delay, the raw condensate in 600 Vt. Water stirred in, where fraction I of the mixed condensate separates out as a resinous mass. This is used for cleaning in 120 Vt. Ethylenglykolmonomelhyläther dissolved and stirred in this solution in 750 Vt. Isopropanol precipitated again, the precipitate sucked off and dried in the air. Fraction I: 5.3 Gt. a mixed condensate as methanesulfonate, which, according to analysis, contains approx. 1.5 units of 4-Nltro-diphenylamine per diazo group (N 11.6%, ND 3.8%, S 4.8%, atomic ratio 6.08: 2: 1.1).

The filtrate from the first precipitation (fraction I) is converted into one by adding zinc chloride and sodium chloride Fraction H obtained by redissolving in water and adding zinc chloride and sodium chloride is dropped. Yield: 8.0 pbw.

Fraction II: A mixed condensate which binds about 0.5 moles of 4-niiro-dlphenylamine per mole of diazo compound contains. (N 8.2%, ND 4.1%, Cl 29.2%, Zn 5.1%, atomic ratio 4: 2: 5.6: 0.54)

Example 2

14.6 Gt. 4-methyl-dlphenylamine (component B, no. 5, table I) are at 80 ° C in 120 Vt. 86.7% longer Dissolved phosphoric acid. After cooling to 40 ° C one carries 25.8 pbw. 3-methoxy-dlphenylamln-4-dlazonlum phosphate (diazo 2, phosphate, Table 1), stir until everything has dissolved and cool to room temperature. At this temperature a solution of 4.8 pbw. Paraformaldehyde In 48 Vt. 86.7% long phosphoric acid added dropwise with stirring and stirred for a further 15 hours. The raw condensate is completely soluble in water. To separate out the condensate, the reaction mixture is diluted with 440 parts by volume. Methanol and leaves in 6000 Vt. Pour in isopropanol. The full-length suspension is heated to 40 ° C. with stirring until it is slightly settles as soon as the stirrer is switched off. The precipitate is sucked off, twice in 1000 Vt. Isopropanol suspended and washed and dried in vacuo at 40 ° C. Yield: 32.5 pbw. The mixed condensate, the M present as acid phosphate, according to analysis, contains about 0.75 moles of 4-methyl-dlphenylamine per mole of diazo compound built-in. (C 48.4%, ND 4.6%, P 10.8%, atomic ratio 24.5: 2: 2.12)

On the superficially saponified cellulose acetate carrier, an analogous catfish can be produced with the same success.

25th

mixed condensate provided, but in which 20% of the 4-methyl-dlphenylamine is caused by dlphenylamine have been replaced.

Example 3

The procedure is as described in Example 2, but with the following amounts of starting material: 73 pbw. 4-methyl-diphenylamine (Component B, No. 5, Table 1), 80 Vt. 86.7% phosphoric acid, 25.8% by weight 3-methoxydlphenyl amine-4-dlazonium phosphate (Diazo 2, phosphate, Table 1) and 3.6 pbw. Paraformaldehyde in 32 Vt. 86.7% long phosphoric acid. 400 Vt. Methanol and 5000 Vt. Isopropanol, for evidence see 2 times 600 Vt. Isopropanol used. Yield 33.2 pbw. The mixed condensate, which as acid phosphate is present, according to analysis, contains about 0.42 moles of 4-methyI-dlphenylamine incorporated per mole of dlazo compound. (C. 43.5 *, ND 5, 19b, P 12.4%, atomic ratio 19.9: 2: 2.2)

Example 4

242 Gt. 3-Methoxy-dlphenylamln-4-dlazonlumchlorid (Diazo 2, Chlorid) are in a mixture of 265.5 Gt. 93% long phosphoric acid and 8.55 parts by weight Dissolved water, and 29.7 pbw of the solution. Paraformaldehyde added. It is condensed at 40 ° C for 48 hours. The reaction mixture is concentrated into three equal parts. In one of the specified amounts of a phenol solution is added dropwise to each of the three parts, which consists of 18.8 pbw. phenol (Component B, No. 8, Table 1) and 4.4 wt. Water has been produced:

1 5.22 Gt. = 0.15 mol phenol / mol dlazo compound

2 6.97 Gt. = 0.20 mol phenol / mol dlazo compound

3 8.64 Gt. = 0.25 mole phenol / mole diazo compound

After each drop, condensation is continued for 3 hours. The raw condensates obtained are clearly soluble in water.

Example 5

In 63.4 Gt. 86.7% long phosphoric acid is 6.6 pbw. Paraformaldehyde stirred in. Then 46.3 Gt. Diphenylamine-4-dlazonlumchlorld (Diazo 1, chloride, Table 1) entered. After two hours of condensation at 40 ° C one carries 6.2 pbw. a phenol-water mixture (weight ratio 9: 1) and condenses 17.3 hours at 40 ° C. A crude condensate which is clearly soluble in water is obtained.

Example 6

4.6 Gt. Diphenylamine-4-dlazonlumchIorld (Diazo 1, Chloride, Table 1) together with 3.3 pbw. 4-hydroxy-cylmamic acid (Component B, No. II, Table 1) In 30 Vt. Methanesulfonic acid (90%) at room temperature solved. In the solution, cooled to + 3 ° C, slowly 1.2 pbw. Paraformaldehyde at this temperature and then condenses for a further 30 minutes at the same temperature. The raw condensate is Clearly soluble in water at this stage. The reaction mixture is without delay with 10 Vt. Methanol under Cooling diluted and stirring in 400 Vt. Isopropanol precipitated. The precipitation is repeated 2 times in 200 each Vt. Isopropanol suspended, suction filtered and dried in vacuo. Yield: 7.4 pbw. The mixed condensate

Ί5 (methanesulfonate) contains about 1 mole of 4-hydroxy-zlmtsaure incorporated per mole of diazo compound. (C 52.4%, ND 5.1%. S 6.3%, atomic ratio 24: 2: 1.08)

Example 7

5 »12 Gt. Dlphenylamine-4-dlazonum sulfate (97.6%) (Diazo 1, sulfate) and 5.6 pbw. 4-Nltrophenol (component B, no. 10) are used at room temperature in 25 Vt. 96% long sulfuric acid dissolved. The solution is quickly cooled to + 5 ° C, and then 2.4 pbw. Paraformaldehyde entered, the temperature being kept at + 5 ° C to + 10 ° C. The mixture is stirred for a further 3 hours at the same temperature and the condensate is then brought into 500 vt. Isopropanol as sulfate for separation. After washing 4 times with 200 Vt. Isopropanol, the precipitate is filtered off and dried in vacuo. Yield: 17.1 pbw. According to analysis, about 0.8 moles of 4-Nltrc-phenol have condensed into the product per mole of dlazo compound. (C 47.0%. ND 5.7%, S 1.1%, atomic ratio C: ND: S = 19.25: 2: 1.18)

Example 8

0.78 Gt. Benzene (component B, no. 14) in 100 Vt. Methanesulfonic acid (90%) dissolved, then you wear 6.17 Gt. Dlphenylamine-4-dlazonum sulfate (95'Mg) (Diazo 1, sulfate) and, as soon as everything is dissolved, add below Stir 1.2 Gt. Paraformaldehyde too. Without delay, pour a previously prepared, 100 "C warm solution of 1.78 parts by weight phenanthrene (component B, no. 15) in 20 parts by weight glacial acetic acid and condensed (>> 14 hours at room temperature. A raw condensate which is clearly soluble in water is obtained, i.e. a real mixed condensate. The condensation product can in known catfish, e.g. B. by adding saturated saline solution, precipitated as chloride and isolated. Yield: 4.5 eq. The product contains some table salt. (C 60.7%, N 9.0%. Aiomvefhaltnls 23.6: 3)

Example 9

11.3 Gt. Mesitylene (component B, no.16) are added to 100% by weight of 80% sulfuric acid at +5 "C with vigorous stirring. An intimate mixture of 32.3% by weight is added to the mixture within 20 minutes while vigorously stirring. S-Msthoxy-dlphenylamln ^ -dlazonlumsuIfat (Diazo 2nd sulfate) and 6 parts of paraformaldehyde, avoiding a rise in temperature above + 12 ° C. After one hour of stirring at +10 to +15 ⁰ C, in 4000 Possibly ice water is added and then ^{heated to 60 °} C. in order to bring everything into solution. In known catfish, the zinc chloride double salt is separated from the solution clarified over charcoal by adding zinc chloride and sodium chloride After drying, dissolved in 260 parts by volume of dimethylformamide, filtered off from salts and precipitated again by stirring in 2000 parts by volume of isopropanol, washed well with isopropanol and dried in vacuo at 40 °. Yield: 23.2 parts by weight of the condensation According to analysis, sat contains about 0.7 moles of bonded second component per mole of diazo compound. (C 56.4%, N 9.4 », atomic ratio 21: 3)

Example 10

At room temperature, In 100 Vt. 80% long sulfuric acid 30 pbw 97.6% diphenylamine 4-dlazonium sulfate (Diazo 1, sulfate) dissolved and 5.4 pbw. Anisole (component B, No. 17) distributed by vigorous stirring. Under vigorous stirring at 20 ° C within 10 min. 4.5 pbw. Paraformaldehyde and stir for a further 1 hour Room temperature, then 2 hours at 40 ° C. To separate the condensate, it is diluted with 120 Vt. Methanol, stirs in 2400 Vt. Isopropanol, suctioned off and washed twice with 1200 Vt. Isopropanol after. It is dried in vacuo at 40 ° C. Yield: 30 pbw. The mixed condensate, which is present as sulfate, According to analysis, contains about 0.5 moles of incorporated second component per mole of diazo compound. (C 51.3%, N 10.7%, Atomic ratio 16.8: 3)

You can also work up. By removing the raw condensate in 2000 Vt. Water dissolves and the mixed condensate precipitates in known catfish with zinc chloride and sodium chloride.

Example 11

In 50 Vt. 86.7% of phosphoric acid is 6.9 pbw. 2-phenoxy-ethanol- (l) (component B, No. 18) and 16.2 Gt. S-methoxy-dlphenylamine ^ -dlazonlumphosphat (diazo 2, phosphate) dissolved at room temperature.

It carries 3 pbw at room temperature with stirring. Paraformaldehyde and condenses for 16 hours at 40 ° C. The raw condensate without leaving a residue is diluted with the same volume of methanol and the product by stirring in this mixture in 1200 Vt. Isopropanol precipitated. You vacuum quickly, wash under slurry twice m .. 500 Vt. Isopropanol and dried in vacuo at 40 ° C. Yield 22.7 pbw. According to analysis, the mixed condensate contains about 1 mole of incorporated second component per mole of diazo compound. (C 46.4%, N 7.0%, P 8.7%, atomic ratio 23.2: 3: 1.68)

A similar condensation product can also be obtained. By following the given above Working catfish the following raw materials condensed with each other for 16 hours at 40 ° C:

32.3 Gt. 3-Methoxy-dlphenylamine-4-dlazonum sulfate (Diazo 2, sulfate), 13.8 pbw. 2-phenoxy-ethanol (component B, no. 18), 60 Vt. 86.7% lge phosphoric acid, 6 pbw Paraformaldehyde. The raw condensal is in 400 Vt. Dissolved water, the solution filtered through activated charcoal and after warming to 40 ⁰ C with 50 Vt. 50% longer zinc chloride solution slowly precipitated.

The precipitate is filtered off with suction, washed with 5% sodium chloride solution and dried in vacuo. Yield 54 pbw According to analysis, the mixed condensate contains about 1 mole of the second component per mole of diazo compound bound. (C 48.0%, N 7.3%, atomic ratio 23: 3)

Example 12

In 20 Vt. Methanesulfonic acid (90%) are 3 pbw. Phenoxyacetic acid (component B, No. 19) with stirring dissolved at 60 ° C. It is cooled to room temperature, 4.6 pbw. Dlphenylamln 4-dlazonlumchlorld (Diazo I, Chloride) in the mixture and slowly contributes 1.2 parts by weight under Rübren. Paraformaldehyde, with an increase the temperature above 40 ° C is prevented by occasional cooling with a cold water bath. Man stirs for a further 3 hours at room temperature. A crude condensate which is easily soluble in water is formed. To the Separation of the mixed condensate, the crude condensation mixture is diluted with 20 pbv. Methanol and leaves with good stirring in 400 Vt. Pour in isopropanol. One sucks off quickly, washed with slurry 2 times with 150 Vt. Isopropanol and dries without delay in a vacuum at 40 ° C. 6.9 parts by weight. That as The mixed condensate present in methanesulfonate contains approximately 1.4 moles per mole of diazo compound according to analysis Second component bound. (C 55.2%, N 7.4%, atomic ratio 26.2: 3)

Example 13

4.84 Gt. 3-methoxy-dlphenylamine 4-d! Azonium sulfate (diazo 2, sulfate) and 3.0 pbw. Sebacic acid lamld (Component B, No. 27) In 30 Vt. 90% longer methanesulfonic acid dissolved. Then you set 0.9 Gt. Paraformaldehyde to and condense! 45 hours at room temperature.

The raw condensate is in 300 Vt. Dissolved water, the solution over 1 Gt. Activated charcoal filtered, and from the Flltrat is the condensate by adding 30 Vt. 50% zinc chloride solution precipitated. The severed one Precipitation is again used for cleaning in 500 Vt. Water dissolved and precipitated again in the same catfish. yield

5.9 Gt. The analysis speaks in favor of incorporating a second component, but there appears to be a certain degree of saponification to have occurred by carbon amd groups. (C 39.3 *. N 8.2SK, ND 4.02%, atomic ratio 23.8: 4.07: 2)

⁵ Example 14

17.75 Gt. In 150 Vt. 86% phosphoric acid dissolved. Then you wear 11.2 Gt. Dimethylol terephthalic acid diamide (component B ₁ , No. 30) as a fine powder with vigorous stirring and condenses for 21 hours at room temperature. The raw condensate is in 1000 Vt. Dissolved water at 40 ° C, and the solution is separated with 200 Vt. 50 »ger zinc chloride solution from the condensation product. The double salt is separated, in 500 Vt. Dissolved water (50 ^° C.) and precipitated again by adding zinc chloride. Yield 26.8 pbw. (C 46.6, N 11.5 »). After analysis, the product contains the elements N and C in a ratio of 5: 23.6.

Example 15

6.5 Gt. S-methoxy-dlphenylamine-i-diazonium phosphate (diazo 2, phosphate) are in 60 W ₁ . 86.7% long phosphoric acid dissolved at 40 ° C. The mixture is cooled to room temperature and a solution is quickly left with thorough stirring

of 3.4 Gt. a.ö-DlmethyloM-methyl-phcnoI (component Bi, no. 31) in 7 Vt. Run into N-methylpyrrolldone. It is cooled so far that the temperature of the mixture does not rise above 50 ° C. One kov-fenslert afterwards 2 hours at 40 ° C. A raw kor.densate which dissolves in water without residue is obtained. For the separation of the The condensation product is the raw Kindensationsgemlsch In 1000 Vt. (Sopropanol stirred in, the precipitate sucked off, with twice 200 Vt. Washed isopropanol and dried. Yield: 7.5 pbw You get that

acid phosphate of a condensate which, according to analysis, has an excess content compared to uncondensed dlazo compound of about 9 carbon atoms per dlazo group. According to this, about 1 mole per mole of dlazo compound Second component condensed. (C 47.3%, N 7.6%, ND 5.1%, P 9.4%, atomic ratio 21.7: 3: 2: 1.67)

³⁰ Example 16

In 100 Vt. 86% longer phosphoric acid is 32.3% by weight. 3-methoxy-dlphenylamine-4-diazonium sulfate (Diazo 2, Sulfate). While stirring, you carry 19.4% in small portions. Bis- (hydroxymethy!) - durol (component Bi, No. 33) at room temperature and condensed for 25 hours at room temperature.

The raw condensate is in 1000 Vt. Dissolved water, a somewhat cloudy solution being obtained. This will Clarified by pressure filtration. The chloride of the condensation product is precipitated by collecting the filtrate 70 ° C heated and 220 Vt. Hydrochloric acid (36% hydrochloric acid diluted with the same volume of water) is added. To clean it, the same catfish is dropped again. Yield: 33.8 pbw. The condensation product has after analysis, compared to the uncondensed dlazo compound, an additional content of about 13 carbon

atoms per diazo group. This corresponds to a ratio of about 1.1 moles of second component per mole Dlazc connection. (C 65.0'v ,, N 8.7%, Cl 9.2%, atomic ratio 26.1: 3: 1.25)

Example 17

In 55 Vt. 86% phosphoric acid is 17.8% by weight. 3-Methoxy-dlphenylamine-4-diazo-lura sulfate (Diazo 2, sulfate) dissolved. Now slowly add 10% while stirring. Finely powdered 4-methyl-2,6-bs- (hydroxymethyl) anlsol (component B ₁ , no. 32; to. Stirring is then carried out for 5 hours at room temperature and 8 _1/2 hours at 40.degree. C., and then is left to stand for 30 hours at room temperature. The condensation mixture is dissolved in 300 parts by volume of water (clear solution), and the condensate is mixed with 150 parts by volume of saturated cooking oil while stirring at + 5 ° C.

solution please. The precipitation is separated and unprecipitated again in the same catfish. 18.7 pbw is obtained. one condensation product that tends to stick together, which, according to analysis, is compared to the uncondensed dlazo compound has an excess content of 11.2 carbon atoms per dlazo group. That corresponds to one Ratio of about 1.1 moles of second component per mole of dlazo compound. (C 60.3 "$, N 8.7% Cl 10 2% atomic ratio 24.2: 3: 1.38)

Example 18

15.42 Gt. Dlphenylamine-4-dlazonum sulphate (Diazo 1, sulphate) (95% Ig) are used in 100 Vt. Methanesulfonic acid

(90% Ig) dissolved. 6.8 pbw are then added with thorough stirring. finely powdered 1,5-Bls- (acetoxymethyl) -naph-

thalin (component B ₁ , no. 37). After an hour and a half of condensation at room temperature, that is

Raw condensate clear Soluble in water, you now carry 4.15Gt. 1,3.DlmethyM, 6 »dImethylol.benzo! (Component

Β ,, No. 35) into the mixture with thorough stirring and condense for a further 45 minutes at room temperature.

The raw condensate is in 500Vt. V / ater dissolved (clear solution). The condensation product is precipitated at +10 "C. by adding 200 Vt. Hydrochloric acid (36.5% acid, diluted with the same volume of water). For purification, it is dissolved in water and precipitated again as chloride by adding hydrochloric acid. Yield: 14.5 pbw.

According to analysis, the condensate product shows de. unconditional dlazo connection a multi-hall of 10.7 carbon atoms per Dla / .ogruppc. (C 67.2%. N 10.4%, atomic envelope 22.6: 3)

28

Example 19

32.4 Gt. 3-Methoxy-dlphenylamln-4-dlazonlumsulfal (Diazo 2, SuIIaD are dissolved in 320% 86% phosphoric acid. Starting with an internal temperature of 25 ° C, 44.5 pbw , no. 36) In felnstgepulvertcr form registered under pipes. I h. stirring is continued without warming, then 20 h. condenses at +40 ⁰ C. one obtains in water clearly soluble crude condensate.

The condensation product is precipitated from the aqueous solution of the crude condensate with hydrochloric acid and for further cleaning dissolved again in water and filled again with hydrochloric acid. Yield 64 pbw (C. 68.2 *, N 5.1 *, atomic ratio 46.8: 3). The analysis result suggests an incorporation of about 2.4 mol Second component per mole of Dlazo compound.

Example 20

At a resolution of 3.4 Gt. 2'-Carboxy-dlphenylamine-4-dlazonium phosphate (Diazo 4th phosphate) In 20 Vt. Is • 90% methanesulphonic acid is gradually added 2.8 pbw with stirring. Bls-acetoxymethyl-durol (component B ₁ , No. 34) is added at room temperature and the mixture is stirred for 24 hours at room temperature.

The clear condensation mixture is used to isolate the reaction product In 250 Vi. Stir in water. The faeces are sucked off and washed! N 250 Vt. Was dissolved at 50 ° C and added from 50 Vt. 18% hydrochloric acid precipitated again. By briefly heating the suspension to 80 ° C and cooling it the suction wedge of the precipitation is improved. It is filtered off with suction, washed with 1 η hydrochloric acid and dried at 35 ° C. The yield is 3.7 eq. (C 64.0 ", N 8.5%, atomic ratio 26.3: 3). After analysis come in the mixed condensate to 1 mole of Dlazo compound about 1.1 mole of second componentc.

Example 21

33.2 Gt. S-methoxy-dlphenylamln ^ -dlazonlumulfat (Diazo 2, sulfate 97.5% Ig) are in 100 Vt. 86% iger Dissolved phosphoric acid. Within 15 min. are at room temperature 25.9Gt. Methoxymethyl diphenyl chloride (For composition see below) (component B, no. 39) was added dropwise with stirring. A clear one emerges Raw condensate, which is stirred for 1.5 hours at room temperature and 6 hours at 40 "C. The condensate is stored in * 500 Vt. Dissolved water, and the solution is freed from a slight cloudiness by filtration. The condensation product is precipitated with hydrochloric acid. Table salt can also be used for the precipitation. Should a If a product that is as free of phosphoric acid as possible is obtained, it is advisable to put the product in again like catfish to fall over. Yield 37.6 pt. According to the analysis, the condensation product has compared to the uncondensed Dlazo compound has a multiple of 16 carbon atoms per Dlazcmolecule. (C -> 5 61.7%, N 7.4%. Cl 9.3%. Atomic ratio 29.2: 3: 1.5)

The melhoxymethyldlphenyloxld used has the following composition: Diphenyl ether 1.3% Mono-o- (methoxymethyl) dlphenyl ether 2.2% w Mono-p- (methoxymethyl) dlphenyl ether 11.8%

unknown, similar Monomethoxymethyl compound 3.9%

o, p'-Dl- (methoxymethyl) dlphenyl ether 21.9%

p, p'-Dl- {methoxymethyl) dlphenyl ether 47.3%

Trl- (methoxymethyl) dlphenyl ether 1.3% « Tetra (methoxymethyl) dlphenyl ether 9.5%

If melhoxymethyldlphenyl oxide is added to the acid without the presence of a dlazo compound, it dissolves this up first with rapid stirring. After seconds to minutes, however, an in and in insoluble condensate from boiling water. A mixed condensate, the exposure products with the same Oleophilic is obtained. By using the diazo 2 instead of the sulphate with otherwise the same working conditions equimolar amount of Diazo 1. Sulphate, used. The mixed condensate containing Diazo 2. However, yeasts copy layers with better shelf life.

Example 22

in 600 Vt. 86% phosphoric acid is 4.65 parts by weight. Diphenylamine 4-diazonium sulfate (95%) (Diazo I, sulfate) solved. You now solve 4.65Gt. 1,4-Bls- (a-hydroxybenzyl) -benzene (component Bi, No. 45) In 30Vt. Glacial acetic acid and warms up just so much that everything goes into solution. The hot acetic acid solution now becomes the strong poured stirred diazo solution. The condensation is carried out for 21 hours at room temperature. The condensation mixture is * o in 2000 Vt. Dissolved water, filtered clear and with 300 Vt. concentrated hydrochloric acid precipitated. The precipitation is separated, in 500 Vt. Dissolved water at 60 ° C, filtered and with 50 Vt. 6 η hydrochloric acid precipitated in water. The detached Product is turned over again in the same catfish. The result is 4.8 pbw. of the chloride of the condensation product. According to analysis, the ratio C: N: Cl = 26.6: 3: 1.05. That corresponds to a ratio from about 0.73 Mo! Dual component per Mon! Diazo compound. (C 69.2%, N 9,! *, C! 8,!%)

29

Example 23

In 1000 Vt. 86% of phosphoric acid are 30.84 pounds. Dlphenylamine-4-dlazonum sulfate (95961g) (Diazo I, sulfate) dissolved. Within 1 hour, with thorough stirring, a dissolution of 18.4 pbw. Benzhydrol (component B ₁ , No. 44) In 200 Vt. Glacial acetic acid dripped in. The condensation is carried out for 24 hours at room temperature. A clear crude condensate which is soluble in water without residue results. Half of the raw condensate is In 2SOOVt. entered water heated to 40 ° C. After initially clear dissolution, the condensation product crystallizes out in the form of crystal leaves on cooling. Yield 21.9 pbw. (C 56.6%, N 8.1%, P 8.9%, atomic ratio 1 ^ .5: 3: 1.5)

According to the analysis, the condensation product has a higher content than the uncondensed compound of 12.5 carbon atoms pm dlazo group. This corresponds to a ratio of about 1 mole Second component per mole of diazo compound.

The second half of the raw condensate is 1.5 Gt. Paraformaldehyde added and 20 hours at room temperature

i * temperature post-condensed. The raw condensate is in 2000 Vt. Dissolved water and slightly cloudy freed by filtration. The condensation product no longer crystallizes out of the aqueous solution. It Can be deposited in normal catfish as Zlnkchlorld double salt. Yield: 22.9 pbw. (C 59.9%, N 8.5%,

Atomic ratio 24.6: 3).

«' Example 24

For the production of the raw condensate one carries In 39.9 Gt. 86% lge phosphoric acid 11 pbw 3-methoxy-dlphenyiamine-4-dlazonum sulfate (Diazo 2, sulfate) and cools to room temperature. Now one drips 5.17 Gt. one In its composition given in Example 21 mixture of methoxymethylated diphenyl ether (Component Bi, No. 39) and stirred for one hour at room temperature.

It is now heated to 40 ° C., and a mixture of 22.1 parts by weight is added. of the same diazo compound with 2.4 pbw. r> araformaldehyd and condensed to 24 hr. at 4O ⁰ C. The crude condensate is used directly for the preparation of the coating solution.

M. Example 25

To produce the Dlazokondensatlonsproduktes one dissolves 81 pbw. Diazo 2, sulfate in 500 Vt. 85% long phosphoric acid, carries 61 Gt within 15 minutes. 1,3-Isopropyl-4,6-dlmethylol-benzene (component Bi, no. 36) and condenses for 39 hours at 40 ° C. The condensation mixture, which is clearly soluble in water, is in 2500 Vt. water solved and with 500 Vt. 18% aqueous hydrochloric acid precipitated again. After vacuuming and washing with 0.5 η hydrochloric acid was air-dried. Yield: 113 pbw. of the chloride of the condensation product. (C. 66.2%, N 8.8%, atomic ratio 26.3: 3)

According to the results of the analysis, approximately every second component is bound to the diazo compound.

40 Example 26 (Verglelchsbelsplel)

By condensation in 80% sulfuric acid of equimolar amounts of diazo I, sulfate, and formaldehyde Dlazo resin obtained analogously to the process given in DE-PS 5 96 731 in the form of the Zlnkchlorld double salt.

Example 27

4.84 Gt. S-methoxy-dlphenylamine ^ -dlazonlumphosphat (diazo 2, phosphate) and 4.4 pbw. Diphenylamine 4-diazonium phosphate (Diazo 1, phosphate) are sold in 300 Vt. 86% dissolved phosphoric acid. Under violent

so stirring is added dropwise 6 pbw. 2,5-bis- (ethoxymethyl) -thiophene (component Bi, no. 42). The mixture turns reddish in color, but remains clear. The condensation is carried out for 2 _1/2 hours at room temperature. The raw condensate is clearly soluble in water.

To separate out the reaction product, the mixture is left in well-stirred isopropanol at about 65.degree run in and cool to room temperature. The precipitate is filtered off with suction and washed thoroughly with isopropanol and dried. Yield: 10.9 pbw. According to the analysis, the condensation product is present as acid phosphate the components 3-methoxy-4-dlazo-diphenylamine, 4-dlazo-dlphenylamine and thiophene Im Built-in ratio of 0.7: 0.3: 2. (C 46.9%. N 6.7%. S 10.1%, OCH, 3.1%, atomic ratio 24.6: 3: 1.98: 0.73) If 2,5-Bls- (ethoxymelhyl) -thlophen is allowed to run into phosphoric acid in the absence of the diazo compound, so a homocondensate of this compound which is practically insoluble in acid and water is obtained immediately.

Example 28

In 60 Vt. 93% phosphoric acid is 3.6 pbw. 2.5-Dimethoxy-4-phenoxy-benzoIdiazon! Umchlorld (Diazo 7) dissolved as a double salt with ¹ A mol of zinc chloride (containing NaCl, N = 7.7%). Dry air is passed through the solution until no more hydrogen chloride escapes. It will then be 2.7 Gt. 1,3-Dllsopropyl-4,6-dl- (methoxymethyl-benzene (component Bi, No. 46) was added and the mixture was condensed for one hour at room temperature and 2 hours at 40 ° C. The condensation mixture was dissolved in water, in which it was clearly soluble and the condensate is precipitated with zinc chloride, separated off and dried. Yield 2.9 pbw (C 57.6%, N 4.4%, atomic ratio

30th

30.6: 2). The analysis shows that in the pulp condensate about 1.2 moles of second component per mole of dlazo compound are bound.

Example 29

3.6 Gt. of the Dlazonlum salt used as starting material in Example 28 (Diazo 7, Zlnkchlorld double salt) In 60 Vt. 90% lger methanesulfonic acid is dissolved, and dry air is passed through the mixture until no more hydrogen chloride escapes.

Then you carry 2.7 Gt. 1,3-Di-Isopropyl-4,6-Bls- (methoxymethyl) -benzene (Component Bi, No. 46) a and condenses for 1 hour at room temperature and 2 hours at 40 ° C.

The mixture is introduced into water and dissolved by adding charcoal and sucking off Shares exempt.

The condensation product is precipitated as Zlnkchlorld double salt from the filtrate. Yield 5.8 pbw (C. 41.0%, N 2.7%, atomic ratio 35.3: 2). This corresponds to a content of approx. 1.5 moles of the second component per Moles of diazo compound.

Example 30

1.75 Gt. 4- (2,5-Dläthoxy-benzoylamlno) -2,5-dläthoxy-Benzoldlazonlumchlorld, Zlnkchlorld double salt (N = 4.8%) (Diazo 8) in 10 Vt. 90% longer methanesulfonic acid dissolved, and dry air is passed through the mixture until no more hydrogen chloride escapes. Then 0.14 Gt. 1,4-bis-hydroxymethylbenzene (Component Bi, No. 38) added. After 4 hours of condensation at room temperature, with Diluted water, filtered and the condensate precipitated from the filtrate with zinc chloride solution.

Yield 2.2 pbw (C 25.2%, N 3.6%, atomic ratio 24.5: 3)

Example 31

In 10 Vt. 90% long methanesulphonic acid dissolves 0.78 pbw. S-Methoxy-dlphenylenoxld ^ -dlazonlumchlorld as a double salt with Vi mol Zlnkchlorld (N 7.2%) (Diazo 9) and passes dry air through the mixture until no more hydrogen chloride escapes. Now you wear 0.14 Gt. 1,4-Dlmethylol-benzene (component Bi, no. 38) a x and condensed 4 hrs. At room temperature. The separation of the condensation product is carried out with zinc chloride. Yield: 1.4 pbw.

(C 22.4%, N 2.9%, atomic ratio 18: 2). The analysis speaks in favor of the incorporation of about 0.6 mol of the second component per mole of diazo compound.

35 Example 32

16.2 Gt. S-Methoxy-dlphenylamln ^ -dlazonlumsuifal (Diazo 2, sulfate) are in 100 Vt. 9.3% phosphoric acid solved. Separately, you mix 8,6 Gt. p-toluenesulfonic acid amide (component Bi, no. 25) and 22.5 pbw. 40% aqueous formaldehyde solution and the mixture briefly boils. A tough condensation product separates out away. After 10 minutes of heating on the steam bath, it is cooled down and the one above the resin The solution poured off. The resin is kneaded with 10 Vt. Water washed. After pouring off the washing water will »the Harz In 8 Vt. added hot methanol and the cloudy mixture in the vigorously stirred Dlazo solution poured. After 2.5 hours of condensation at 40 ° C and standing for 1 hour at room temperature a solution is obtained in which an undissolved white substance is suspended in moderate amounts. By With suction through a plastic filter, a clear condensate is obtained, which is clearly soluble in water. From the solution of the filtrate in 250 Vt. Water is added by adding 210 Vt. saturated aqueous saline solution the condensation product precipitated as a viscous mass. After this by falling into the same catfish Once cleaned, it is dried over phosphorus pentoxide in a vacuum to form a friable solid product. Yield: 7.6 pbw. (C 52.2%, N 11.5%, S 4.5%, atomic ratio 21.2: 4: 0.685) so

The analysis result suggests that the condensate contains units of the diazo compound and the second component present in a ratio of 1: 0.7.

', Example 33

According to Example 1 of DE-PS 11 38 401, a condensation product of S-methoxy-dlphenylamine ^ -diazoniumchlorld is used and formaldehyde and deposited as acidic phosphate that still contains some phosphoric acid. (N 9.3%; atomic ratio C: N: P = 14: 3: 2.3)

The product has an average degree of condensation of about 3 units of methoxydlphenylamine diazonium salt per molecule, determined by the cryoscopic determination of the molecular weight of the diazoamine compound with Dllsobutylamln In Benzene.

10 Gt. of the Dlazokondensatlonsprodukts in 85 Gt. 85% phosphoric acid dissolved. Within 10 min. drips one 5,7 Gt. 4,4'-Bls-methoxymethyl-dlphenylether (component Bi. No. 41) and condenses for 20 hours without Heat supply. The clear condensation mixture, which is clearly soluble in water, is charged at 100 pbv. Water diluted and this solution with 330 Vt. saturated aqueous sodium chloride solution added. The precipitation is made by redissolving Purified in water and reprecipitation with saline solution and the separated product dried.

Yield: 8.1 pbw. (C 48.3%, N 4.3%, atomic ratio 39.4: 3) According to the analysis, the dlazo homocondensate and the second component are approximately in a molar ratio of 1: 5.4

mixed condensed with each other.

Example 34

In 40 Vt. 80% sulfuric acid are 5 Eq. 4-p-Tolylmercapto-2,5-dlrnethoxy-benzoldlazonlurnchlorld, Zinkchlorld double salt (N 6.9%) (Diazo 6) is dissolved, and dry air is passed through the solution until no

More hydrogen chloride escapes.
0.88 Gt. 1,4-Bls-hydroxymethyl-benzene (component Bi, No. 37) are added in portions and the mixture is stirred

another 1 hour at room temperature and left to stand overnight. One now carries in 300 Vt. Water in, uses ο Removal of a small amount of turbidity 2 Gt. Charcoal is added, suctioned off and the condensation product falls in the clear filtrate with zinc chloride and table salt. Yield: 5.4 pbw. air dry (C 31%, N 3.5%, atomic ratio 20.6: 2).

According to this, the condensate contains about 0.7 moles of the second component per mole of Dlazo compound.

Example 35

In 265 Gt. 93% phosphoric acid is 32.3 pbw. 3-Methoxy-dlphenylamine-4-dlazonum sulfate (Diazo 2, sulfate) dissolved. One now drips 25.8 pbw. 4,4'-Bls- (methoxymethyl) -dlphenylether (component B ₁ , no. 41) and condensed for 2 hours at 40 ° C. 16 pbw. Paraformaldehyde, condenses for a further 6 hours at 40 ° C and left to stand overnight at room temperature. The return in water

^<N standsios iösiiche mixture is dissolved in water and added to the solution with saturated sodium chloride solution. The voluminous precipitate is kept at 40 ° C. for 1 hour and finally suctioned off as much as possible and the Nutscheti contents, a green paste, are dried over phosphorus pentoxide. The product is transformed into a tough, green mass that smells strongly of formaldehyde. Yield 175 pbw (C 16.4%, N 1.9%, S 0.45%, P 13.7%, atomic ratio C: N: P = 30.2: 3: 9.7). The condensate shows opposite the uncondensed Dlazo-

²⁵ compound has an additional content of about 17 carbon atoms.

Example 36

A coating solution of 0.8% of the Mlschkondcnsatlonsprodukts described below and 1 mole of HCl per mole

3fi Dlazoniumgruppen In a mixture of 96 Vt. Ethylene glycol monomethyl ether and 4 Vt. Water is on applied a roughened with metal wire brushes aluminum carrier, which according to DE-PS 11 34 093 had been pretreated with polyvinylphosphonic acid. Then the coating is applied with warm air

dried up.

With the reduction of the Feuchtlgkeltsempflndllchkelt of the material, which is characterized by sensitivity to - have to recognize fingerprints ^13, the Entwlckelbarkclt the copying layer is naturally back with water. The developers used are:

Developer ί: 100 Vt. water

5 Gt. Sodium lauryl sulfate (50%) (remainder sodium sulfate) 40 3 Gt. Tartaric acid

Developers: Developer 1, the 2 Gt. Benzyl alcohol are added.

With developer I rubbing and a somewhat longer exposure is necessary, with developer II the development takes place easier and faster.

• »5 The mill condensal used is produced as follows.

4.4 Gt. Dlphenylamine-4-dlazonium phosphate (Diazo 1, phosphate) are sold in 300 Vt. 96.5% long phosphoric acid dissolved, a boiling solution of 4.0 pbw is poured into the solution with thorough stirring. 9,10-bis-methoxymethyl-aitthracene (Component Bi, No. 43) in 30 Vt. Glacial acetic acid. One condenses 1/1 hour without further ado Heat. The raw condensate is soluble in water without residue. To convert the condensation product to Isolle-

so ren. the condensation mixture with 150 Vt. Methanol is diluted and the solution is poured into 2000 Vt. Isopropanol poured in at about 65 ° C. The precipitate is filtered off with suction, washed with isopropanol and dried. Yield: 5.4 pbw. After analysis, the condensate showed opposite to the uncondensed dlazo compound an additional content of 24.4 carbon atoms per molecule of diazo compound, which corresponds to about 1.5 Moles of second component per mole of dlazo compound. (C 52.9%, N 5.1% P! 1.3%, atomic ratio 36.4: 3: 3)

Example 37

An electrolytically roughened aluminum foil is with a 2% aqueous solution of the chloride condensation product produced from diazo compound 2 and component B, no. 40 by tamponing coated. After image-wise exposure through a negative, wiping over with 1.5% strength makes it more aqueous Phosphoric acid developed and colored with bold paint. The result is a high-performance printing form.

A good result is also achieved if the same substrate is coated with a 2% solution of the acid phosphate of the condensation product described in Example 2 In water to which 4% n-butanol added is used. In this case, water is used for development.

An equally powerful printing form is obtained in an analogous way if the first solution is based on a mechanically grained aluminum foil is applied, which in well-known catfish with an alkali silicate has been pretreated.

Instead of the chloride of the condensate product, the corresponding zinc chloride or cadmium can also be used.

32

chloride double salt use. Developer II can be used for development.

The condensation product is prepared in the following way:

In 93.5 Vt. 86% phosphoric acid is 30.2 pbw. 3-methoxy-dlphenylamine-4-dlazonium sulfate (diazo 2, sulfate) dissolved. You then carry 29.3 Gt. fcingepulverten 4,4-Bls-acetoxymethyldlphenyläther (Bi component, no. 40), then stirred for 1 Vi hours. without heating and eventually condensed by still 3'Λ Std. Isei 40 ° C. The clear condensation mixture is! n 500 Vt. Dissolved water (clear solution), and at 40 ° C wlid by adding dropwise 220 Vt. Hydrochloric acid (36% HCl diluted with the same volume of water) precipitated the chloride of the condensation product. For cleaning, it is dissolved in warm water and the chloride is precipitated again by adding hydrochloric acid. It is dried at 30 ° C. in a circulating air drying cabinet. Yield: 38.7 pbw. (C 65.7%, N 8.1%, Cl 8.6%, atomic ratio 28.5: 3: 1.26)

Example 38

A polyethylene terephthalate film roughened by sandblasting is then finely rubbed The coating mixture is coated and the coating is dried on:

~ T, 25% poly-N-vinyl-N-methylacetamine (K value 9I) 0.5 Gt. Hellogen blue B powder (CI 74 160) 0.1 pt. Partial silica

0.375 Gt. of the diazo condensate M given below

IS Gt. water
1.6 Gt. Ethanol

After imagewise exposure under a negative, a blue colored positive is obtained by rinsing with water GerbbÜd received. The diazo condensal is made as follows:

32.4 Gt. 3-Methoxy-diphenylamine-4-dlazonum sulfate (Diazo 2, sulfate) are In 32Q Vt. 85% long phosphoric acid dissolved. In the course of 10 minutes, 16.6 Gt. Very powdered and sieved 1,3-Dlmethyl-4,6-dtmethylol-benzene (component B ₁ , No. 35) is added with vigorous stirring, and stirring is continued for 30 minutes at room temperature. Subsequently, the mixture is condensed for 42 hours with stirring at 40 ° C. The raw condensate is soluble in water without residue. 30 ||

To separate out the condensation product, dissolve the condensate mixture in 1000 pbv. Water, falls by adding 60 Vt. 45% aqueous hydrobromic acid and sucks off the precipitate.

For cleaning, the product is dissolved in 1000 Vt. Water at 50 ° C and falls again by adding hydrobromic acid off, washed with 1% aqueous hydrobromic acid and dried the filtered off Product in the air. Yield: 42 pbw (C 53.1%, N 7.8%, Br 18.6%, atomic ratio 23.8: 3: 1.25). After that are about 1.1 moles of second component bound per mole of diazo compound.

Example 39

A roughened by metal brushes and according to the teaching of DE-PS 11 34 093 with polyvinylphosphonic acid *> precoated aluminum foil is coated with the following coating solution and the coating is dried on.

0.4 Gt. of the condensation product described below

80 Gt. Ethylene glycol monomethyl ether

20 Gt. Butyl acetate

The development of the imagewise exposed material under a negative into a positive printing form takes place with the developer II.

To prepare the condensation product, a dissolution of 3.23 pbw is added. 3-Methoxy-dlphenyl- '° amin-4-dlazonium sulfate (Diazo 2, sulfate) In 12%. 86% long phosphoric acid with good stirring 12.9%. 4,4'-Bls-methoxymethyl-dlphenyl-ether (component B ₍ , No. 41) and condenses for 24 hours at 40 ° C. The clear crude condensate is introduced into 100 vt. 2 η hydrochloric acid, with a tough, sticky After decanting the aqueous mother liquor, this mass is kneaded with a further 100 parts by volume of 2 η hydrochloric acid and the aqueous phase is decanted again.

After drying, the somewhat sticky condensate is used for coating in a vacuum. (C. 64.6%, N 3.4%, atomic ratio 66.5: 3)

Example 40 «

Electrolytically roughened and then anodized and then with polyvinylphosphonic acid according to DE-PS 11 34 093 pretreated aluminum supports are each coated with one of the coating solutions given below coated, and the coating is dried.

33

a) 1.1 Gt b) 1.1 Gt O 1.1 Gt d) 1.1 Gt Mixed condensal (see below) 0.6Gt 0.6 43t 0.6 Gt 0.6Gt Diazo condensate according to DE-PS 11 38 401,
Example 1 adjusted to 2.8 molecules
Phosphoric acid per diazo group 0.2 Gt 0.2Gt 0.2 Gt. 0.2Gt p-Toluenesulfonic acid - HiO 3 Gt - - - Harzl - 3 Gt. - - Resin 2 - - 0.1 Gt - Resin 3 - - 0.1 Gt - Harz 4 = 'Gt. Resin 5

_M ethylene glycol monomethyl ether / 100 Vt. 100 Vt. 100 Vt. 100 Vt Butyl acetate 8: 2 (Vt)

The mixed condensate is obtained as follows:
One dissolves 32.3Gl. 3-Methoxy-diphenylamine-4-dlazonium sulphate (Diazo 2, sulphate) in 170% 85% * low phosphorus

x acid, drops 25.8 pbw. 4,4'-bis-methoxymethyl-dlphenyl ether (component Bi, no. 41) and condenses for 5 hours at 40 ° C. After diluting ml; 250 Vt. The chloride of the condensation product is precipitated in water by adding 220Vt. semi-concentrated hydrochloric acid. The chloride of the condensate is dissolved again in water, and with sodium mesitylenesulfonate, the mesitylenesulfonate of the dlazo compound is obtained as a precipitate which is sparingly soluble in water. Yield: 53 pbw (C 67.2%, N 6.3%, S 4.6%, atomic ratio 37.3: 3: 0.96) The condensation product has a polymer-homologous structure. A mixed condensate produced in practically the same catfish (condensation and work-up conditions below) is converted into the azo dye with l-phenyl-3-methyl-5-pyrazolone and its mean molecular weight is determined. In addition, this dye is fractionated and the average molecular weights of the individual fractions are determined. Production of the mixed condensate:

3-methoxy-dlphenylamine ^ -dlazonum sulfate 32.3 pbw.

86% lge phosphoric acid 170 pbw. 4,4'-Bls-methoxymethyl-dlphenylether (98 to 99%) 25.8 parts by weight

Condensation time 4.5 hours at 40 ° C

40 Separation as chloride 2 χ with hydrochloric acid

Final form of registration Salt of mesitylenesulfonic acid Yield 55 pbw

(C 67.2%, N 6.4 *, S 4.5%, P 0.2%, Cl 0.23%, OCH, 4.9%, atomic ratio C: N: S: OCHj = 36.7: 3: 0.95: 1.04)

10 pbw of this product is converted into ethylene glycol monomethyl ether with the addition of NHj and phenylmethylpyrazolone the dye in a yield of 9.23 pbw. obtain.

The mean molecular weight of the dye is determined by osmometric determination of the vapor pressure of a Solution Determined in chloroform. It is 3180.

For fractionation, chloroform solutions of the dye are applied to aluminum foil and dried. These thin layers of dye are then mixed with a mixture of solvent (chloroform) and non-solvent (Methanol) extracted, starting with poorly dissolving mixtures and then with getting better and better dissolving Mixtures are extracted. About details of the experiment and the mean molecular weights of the The table below provides information on the electorate fractions.

34

chloroform
(ecm) 20th Methanol
(ecm) 24 244 N
% middle MG fraction
No. - 150 fraction
lot
(mg) - - 1 60 90 3.2 - - 2 67.5 82.5 13.9 11.8 1115 3 75 75 65.8 11.8 1451 4th 82.5 67.5 89.6 11.5 1828 5 90 60 91.2 11.3 2530 6th 97.5 52.5 152.6 10.8 4012 7th 105 45 247.3 10.6 6165 8th 112.5 37.5 429.4 10.3 6674 9 156.6

The following resins are used:

Resin 1: epoxy resin based on bisphenol-A - EPLchlorhydrln, melting point 64 to 76 ° C., medium "; Molecular weight 900

Resin 2: polyvinyl butyral, containing 69 to 71% polyvinyl butyral, \% polyvinyl acetate and 24 to 27% polyvinyl alcohols. Viscosity of an oily solution at 20 ° is 4 to (i rnPas (DIN 53015)

Resin 3: non-plasticized urea resin with an approximate acid number of 2

Resin 4: alkyd resin (phthalic anhydride 38%, oil content 30%, acid number less than 10, viscosity (40% in xylene) 550 to 700 mPas

Resin 3: polyvinyl acetate of the average molar weight. 100,000.

The plates are placed under a negative for 2 minutes by means of a xenon pulse lamp of 5 kW at a distance of 1 m exposed imagewise and then by wiping over with a developer of the following composition Converted into printing forms, which is very good, especially in the case of samples a, b and d Show circulation stability.

A mixture of

50 Gt. water

15 Gt. Isopropanol

20 Gt. n-propanol

12.5 Gt. n-propyl acetate

1.5 Gt. Polyacrylic acid

1.5 Gt. Acetic acid.

It is also possible to reinforce the printing forms in known catfish by varnish and on this catfish increase printing performance.

Usable layers are also obtained if the dlazo condensate is added to the coating solutions a to d according to DE-PS 11 38 401, Example 1, omits and the Tokx> isulfonic acid by about 0.5 to 2 moles of phosphoric acid replaced per mole of diazo groups.

Instead of the mixed condensate used, other components made from the same components, but In Use mixed condensates built up in a different ratio, e.g. B. the following:

I)

S-methoxy-diphenylamine ^ -diazonium sulfate (Diazo 2, sulfate)

85% phosphoric acid

4,4'-bis-methoxymethyl-diphenyl ether (component Bi, no. 41)

Condensation time

100 Gt.

527 Gt. 60Gl.

6 hours 40 ° C standing overnight

64.6 Gt.

340 Gt.
77.4 Gt.

4.5 hours 40 ° C

35

continuation

I)

2)

2 x precipitated as chloride and finally deposited as the salt of the

Yield _I0 analysis

¹⁵ atomic ratio:

Mesilylenesulfuric acid
140 gl.

C: 66.5% N: e-, 8% S: 5.2%

OCH ₃ : 34.2: 3: 1

Mesitylenesulfonic acid 126 pbw

C: 69.2% N: 4.9% S: 4.9%

OCH ₃ : 4.9% 49.5: 3: 1.07: 1.35

The average molecular weight of the azo dyes of 2) with methylphenylpyrazolone, determined v / le described above, is 2390.

Example 41

One according to DE-PS 11 34 093 precoated with fblyvlnylphosphonic acid and roughened by metal brushes The aluminum support is coated with the following coating solution.

0.4 Gt. one of the mixed condensates described below 0.0605 Gt. p-toluenesulfonic acid 0.080 Gt. 4-methoxy-4'-dlmelhyIamino-azobenzoI

100 Vt. a mixture of ethylene glycol monomethyl ether and butyl acetate
in a volume ratio of 8: 2

Image-wise exposure through a negative gives a clearly visible positive contrast image. The development to the printing form can be carried out with developer I (example 36).
The mixed condensates are produced analogously to Example 40 as follows:

a)

b)

86% phosphoric acid 4-methoxy-diphenylam! N-4'-dlazonium sulfate (Diazo 3) 4,4'-Bls-methoxymethyl-diphenyloxld (component Bi, no. 41) Condensation time at 40 ° C

The condensation mixtures are clearly soluble in warm water. The condensation products are precipitated as chlorides with hydrochloric acid.

120 Gt. 170 Gt. 32.3 Gt. 32.3 Gt. 12.9 Gt. 25.8 Gt. 20 hours 3.5 Hours.

a) 1 Gt. b) yield 22 5: 3 44.5 Gt. C: N atomic ratio 29 34.2: 3 in the condensation product 64.2% analysis C: 7.6% 65.6% N: 6.7%

The analysis suggests that in case a) about 1.2, in case b) about 1.5 moles of the second component per mole Dlazo compound are mixed condensed.

Examples 2 to 7

In Examples 2 to 7, the usefulness of a number of other mixed condensates as part of the light-sensitive copier layer of copier material for the photomechanical production of offset printing forms shown. Aluminum foil roughened by Mculklruhibursten serves as the carrier, which according to DE-PS 11 34 093 has been pretreated with polyvinylphosphonic acid.

The coating solutions used and details of the mixed condensates used are in Table 3 compiled.

In the vicinity of Example 43, too, the copying layer containing the mixed condensate has a higher sensitivity to light on = ils an equally strong head, which only the corresponding formaldehyde condensate the dlazo compound or a mixture of this formaldehyde condensate with a corresponding amount of one

36

Contains formaldehyde condensate of 4-methyl-dlphenylamine.

For example 45 it should be emphasized that this copier layer, in addition to very good photosensitivity, also
shows very good shelf life. Thus, the previously sealed printing plate can be stored at 100 ° C for hours
can still be copied and developed without the non-minds tending to tone.

In Example 47 it should be emphasized that a printing form can be produced even by a very short exposure. So
gnawed an exposure of 10 to 20 seconds with a 5 kW xenon pulse lamp at a distance for the copy
from 1 m. The printing form can be reinforced with the usual varnishes.

Table 3 Example mixed condenser (MK) Diuzo connection component

AN ₂ XB or Β,

Active Separated as

CO-Ve r-

binding

Empire solution Ratio% MK Other additives Solvent A - NjX: B blends

or B, in MK approx. (parts by volume)

developer

42 Diuzo 10, inner

Sulz

43 Diazo 2, H ₂ PO ₄ "

44 Diazo I, Cl "

45 Diazo 2, HSO ₄ "

46 Diazo 5th HSO ₄ "

CHnO inner salt

CH ₂ OH ₂ PO ₄ H ₁ PO ₄

CH ₂ O CHjSO., 47 - naphthyI- (2) -S0.i 41 Cl "

47 Diazo 11th Cl

- ZnCl;

naphthyl- (2) -S0.r

0.1 - DMF: HO

92: 8

0.1 0.3 ecm 0.1 m ÄGMMÄ / BA /

Phosphoric acid H ₂ O

to 100 ecm 54: 36: 10 solution

0.4 - ÄGMMÄ / BA /

H ₂ O 54: 36:10

0.5 - ÄGMMÄ / BA

80:20

1.0 1.5 moles ÄGMMÄ / BA

Phosphoric acid 80:20 per mole of diazo groups

0.5 - ÄGMMÄ

DMF = dimethylformamide AGMMA - ethylene glycol monomethyl ether

ΒΛ - Buiylucetul

H; O

H ₂ O

0.5 ⁰ O trisodium phosphate in H ₂ O

II (example 36) II (example 36)

II (example 36)

L \ J Z. * t itt

The preparation of the dlazo condensates used in Examples 42 to 47 is described below.

Example 42

In 50 Gt. 80% lger sulfuric acid are 6.1 g. 3,5-Dlmelhyl-anllln (component B, no. 1) was dissolved by heating at 7O ⁰ C. It is now cooled to room temperature, 13.8 wt. of the diazo compound 10 and cools to 0 ° C. To the Krlstallbrel are 3Gl. Paraformaldehyde, dissolved in! 5%. 80% longer sulfuric acid, which creates a clear crude condensate. After stirring for five hours at room temperature and standing overnight, it is in 1000 vt. Entered water, sucked off the precipitate, washed thoroughly with water and dried. Yield MGt. (C 50.9%, N 12.5%, ND 7.4%, S 10.1%, atomic ratio 16.1: 3.38: 2: 1.2)

The analysis suggests a content of about 0.35 moles of second component per mole of diazo compound.

Example 43

Production of the mixed condensate as in Example 2.

Example 44
Production of the rviisLnkunüensais as in Example 12.

Example 45

The procedure is similar to Example 40, but the following applies: 16.2Gt. 3-Methoxy-dlphenylamine-4-dlazonium sulfate (Diazo 2, sulfate), 36Vt. 86% lge phosphoric acid, 6.86%. 4,4'-Bls-methoxymethyl-dlpheriylsulfid «(component B ₁ , no. 47). Condensation 1.5 hours at room temperature and 20 hours at 40 ⁰ C.

The raw condensate is dissolved in water and the condensate product is obtained from this solution by adding hydrochloric acid failed. The tough precipitate is dissolved in water and precipitated again by adding hydrochloric acid. The precipitate is redissolved in water, and this solution is converted into naphthalene-2-sulfonic acid Sodium precipitated the corresponding sulfonate of the condensation product. After drying at 40 ° C 3 » the yield is 12.9 pbw. (C 64.7%, N 6.4%, S 9.1%, atomic ratio 35.4: 3: 1.86).

According to this, about 0.86 moles of second component are incorporated per mole of diazo compound.

An equally good result is obtained under the working conditions of Example 45 when one of the same components but used in different quantities of condensate products.

In this case, condensation takes place as follows: 16.2 Gt. 3-methoxy-dlphenylamine-4-dlazonum sulfate (Diazo 2, Sulfate), 50Vt. 86% lge phosphoric acid and 13.7%. 4,4'-Bls-methoxymethyl-dlphenylsulfld (component Bi, No. 47) are condensed at 40 ° C. for 4 hours. The raw condensate is dissolved in water at a low level The turbidity was freed with activated charcoal, the product was precipitated with saline solution, separated off and washed with saline solution washed. The chloride is dissolved again in water and the condensate as a salt of mesltylenesulfonic acid pleases. Yield: 24.8 pbw. (C 65.9%, N 6.5%, S 10.2%, atomic ratio 35.4: 3: 2.05). The condensate contains -to accordingly, about 1 mole of second component per mole of diazo compound is condensed in.

Example 46

In 60Vt. 93% phosphoric acid is 8.3%. of the diazo compound 5 (sulfate, slightly moist; N 6.2%) dissolved, and within 12 minutes. become 5.2Gt. 4,4'-Bls-methoxymethyl-dlphenyl ether (component B ₁ , no. 41) was added dropwise. The mixture is stirred for one hour without further heating and for two more hours at 40 ° C.

The clear crude condensate, which is clearly soluble in water, is dissolved in water, the condensation product through Addition of aqueous hydrochloric acid and precipitate after redissolving in fresh water again with hydrochloric acid deposited. After drying 10Gt. obtained from the chloride of the condensation product. (C so 62.3%, N 4.3%, atomic ratio 33.8: 2)

This means an incorporation of about 1.1 moles of second component per mole of diazo compound. Example 47

In 10 Vt. 92% long phosphoric acid is 0.94%. the diazo compound 11 (Zlnkchlorld double salt, N 8.9%) dissolved, and dry air is passed through the mixture until no more hydrochloric acid escapes, i.e. H. until that The mixture is largely free of chloride ions.

You now wear 0.52Gt. 4,4'-Bls-methoxymethyl-diphenyl ether (component Bi, no. 41) and condensed 15 hours at room temperature. The condensation mixture is in 100 Vt. Dissolved water, clarified with activated charcoal, «> and with 0.92Gt. naphthalene-2-sulfonic acid sodium in 100 Vt. Water becomes the sulfonate of the dlazo compound pleases. Yield after drying: 0.9 pbw. (C 64.4%, N 3.8%, S 4.8%, atomic ratio 59.3: 3: 1.66)

The analysis shows that about 0.66 molecules of the sodium salt of sulfonic acid were entrained in the precipitation are. Taking this into account, the analysis speaks in favor of a diazo compound condensation ratio to the second component of about 1: 1.75.

Examples 48 to 53

Examples 48 to S3 demonstrate the use of some mixed condensates for the production of planographic printing forms on an aluminum carrier that is only roughened by metal brushes and does not require any further pretreatment has experienced. The details are summarized in Table 4, and the description of the production the dlazomix condensates follow the table.

It is noteworthy that after Examples 48 and 49 positive printing forms were obtained from positive originals will. However, the developer resistance is not particularly high, especially in Example 49. The rest Examples (50 to 53) again provide negative working copy materials, i.e. H. by exposure under negative Templates will receive positive printing forms. While the printing forms produced according to Example 50 a show only moderate acid resistance, the printing plates obtained according to Examples 51 to 53 are very good resistant to aqueous phosphoric acid, even if the condensates are in the form of metal halide double salts be applied. This is shown by the fact that dilute aqueous phosphoric acid is used as a developer.

40

Table 4

example Mixed condensate (MK)
Diazo compound
AN ₂ X , Cl Compo
nent B Active
CO consumption
binding Secluded as relationship
AN ₂ X: B
in MK approx. 7th Streichlösunii
% MK solvent
Mixtures
(Volume parts) ÄGMMÄ developer 48 Diazo 1, Cf 8th CH ₂ O Cf 1 : 2.1 3 ÄGMMÄ (anhydrous) + 0.6%
Na ₃ PO ₄ + 0.15 "ZbNaH ₂ PO ₄
in water 49 Diazo 3, H ₂ PO ₄ " 9 CH ₂ O Cf 1 : 0.75 1 ÄGMMÄ / DMF / H2O
54: 36: 10 15 seconds with 0.5%
Na ₂ HPO ₄ in water,
then treatment with
Emulsionsluck after
DE-PS 1143710 50 Diazo 2, HSO ₄ " 5 CH ₂ O H ₂ PO ₄ "H ₃ PO ₄ 1 : 0.5 0.1 H ₂ O / ÄGMMÄ
9Ii: 2 H ₂ O 51 Diazo 2, Cf 20th CH ₂ O _{r |} - ZnCl ₂ 1 : 0.2 0.5 H ₂ O 2% H ₃ PO ₄ 52 Diazo 3, HSO ₄ " 21 CH ₂ O Cl ₂ 1 . 0.3 0.5 H ₂ O 2% H ₃ PO ₄ 53 Diazo 1. 22nd CH _: 0 HSO ₄ " 1 : 0.5 2% H ₃ PO ₄ - ZnCl: t-l'-i

AGMMA = Alhyleneglycol monomethyl ether
DMF = dimethylformamide

■ fats) F.

The mixed condensates are produced as follows: Example 48

From 25.2 Gt. Diphenylamine ^ dlazonium chloride (Diazo 1, chloride) (92.5% lg), 18.8 pbw. Phenol (component B, No. 8) and 40 Vt. A solution is produced in glacial acetic acid. The solution becomes a mixture at room temperature from 200 Vt. 36.5% aqueous hydrochloric acid, 29.6% by weight 30.4% Iger aqueous formaldehyde solution and 40 Vt. Glacial acetic acid poured in with stirring. After about 1 minute, the reaction product precipitates out as a viscous mass. The mixture is stirred for 10 min. after, the aqueous solution is poured off and the condensate is kneaded 5 times with 200 Vt each time. Water through. For cleaning dissolve the reaction product in 360 vt. Ethylene glycol monomethyl ether and falls by pouring the solution in 4000 Vt. Water to which 40 Vt. 36.5% lge aqueous hydrochloric acid has been added, again from. The precipitation is with Water washed thoroughly and dried, finally in a vacuum over phosphorus pentoxide. A deep yellow falls Resin in an amount of 22 gl. which, according to analysis, has a diazostlckstoffgeha'.t of 2.2%. From this a ratio of about 7 phenol units to each diazo group is calculated.

Example 49

13.6Gt. 4-Methoxy-diphenylamine-4'-dlazonium chloride (Diazo 3, chloride) together with 7.5 "jt. 4-th-butyl-phencl (Component B, no. 9) in a mixture of 49.1 pbw. Methanesulfonic acid (98%) and 49.1 Gt. Glacial acetic acid dissolved, and the solution is cooled to + 10 ° C. At this temperature one drips one Dissolution of 3 Gt. Paraformaldehyde In 20 Vt. 98% longer methanesulfonic acid is added within 10 minutes with stirring. The mixture is stirred for a further 20 minutes at this temperature, allowed to warm to room temperature and stirred for a further hour and finally heats up another 10 MIn. to 40 ° C. The mixture is in 1000 Vt. Stir in water. For cleaning dissolve the precipitation in 200 Vt. Ethanol and falls by stirring into a mixture of 5OVt. 36.5% aqueous hydrochloric acid and 1000 Vt. Water at 70 ° C. The cleaning is repeated in the same way.

It falls a ran yellow colored resin in a yield of 10.3 pbw. at. According to analysis, the condensation ratio of dlazo compound to phenol is about 1: 2.1 (C 67.6%, N 6.3%, atomic ratio C: N = 37.6: 3)

Example 50

Production of the mixed condensate as in example 2.

Example 51

In 36 Vt. 90% methanesulfonic acid are 3.03 pbw. 3-methyl-phenoxymethylphosphonic acid (component B, No. 20) and 9 Gt. Diphenylamine 4-dlazonum sulfate (97.6% Ig) (Diazo 1, sulfate) dissolved. You are now under Cool a solution of 1.4Gt. Paraformaldehyde In 14 Vt. 90% longer methanesulfonic acid is slowly added and heated finally another 3 hours at 40 ° C.

The raw condensal is now with water to 1000 Vt. diluted and from this solution the condensate product precipitated with zinc chloride. Yield 11.6 pbw (C 47.4%, N 9.4%, P 3.3%, atomic ratio 17.7: 3: 0.48)
The mixed condensate therefore contains about 0.5 mole of the second component per mole of Dlazo compound.

Example 52

■ »5 in 40Vt. 80% sulfuric acid dissolves 8.2%. 96.2% total 4-methoxy-dlphenylamine-4'-dlazonlumchlorld (Diazo 3, chloride). A solution of 3.3 pbw is added dropwise to this solution while stirring. 4-chloro-phenoxymethylphosphonic acid (Component B, No. 21) In 10 Vt. N-methyl-pyrrolldon, in which one 1,4Gt. Paraformaldehyde has slurried.

After 1 hour of condensation at 40 ° C, the condensation mixture in 1000 Vt. Isopropanol stirred in, the precipitate sucked off, washed and dried.

Yield: 6.4 pt. (C 46.1%, N 10.8%, P 1.18%, atomic ratio 15.8: 3: 0.16) According to this, the condensation product contains about 0.2 mole of the second component per mole of dlazo compound.

Example 53

The procedure is as in Example 51, but with the following starting materials:

15 Vt. 90% igc methanesulfonic acid
3 Gt. Diazo 1st sulfate (97.6% lg)

M> 0.6 Gt. 4-tert-butyl-phenoxymethylphosphonic acid (component B, no. 22)

0.38 Gt. Paraformaldehyde in 5 Vt. Methanesulfonic acid

The condensation is carried out for 3 hours at 40 ° C. and the product is deposited as Zincchlorld double salt. Yield 3.8 pbw (C 44.8 * .. N 9.3%. P 1.9%, atomic ratio 16.9: 3: 0.28) * 'The condensate accordingly contains about 0.3 mol of intermediate component per mole of delta.

42

Examples 54 to 56

These examples demonstrate the usefulness in principle not only of mixed condensates in dlazonium salt form.
but also that obtainable from these by reaction with sodium azide or with secondary amines
Azides or diazoamino compounds as light-sensitive components of copying layers, in the special case 5 those for the production of tanning images.

The most important data of the examples is given in Table 5.

In all cases, the specified coating mixtures are centrifuged onto the respective carrier,
and the coating is dried on. After moderate exposure, the unexposed areas become -nil
Detached water and, after drying, the cross-linked image areas are colored with aqueous crystal violet solution.

43

Table 5 (MK) 41 Active Secluded relationship carrier Brush solution solvent developer M.
O Dimeihyllomiamide Example mixed condensate component CO consumption as AN ₂ X: B % MK Further additions Mixtures Diazo BB ₁ binding or Bi approx. (Volume parts) Water "^" link will be in 10 Vi. water CH _: 0 inner salt 1: 1 ÄGMMÄ / BA / H2O A-NjX 13th electrolytic 0.6 0.11Gt. NaN, / 72: 18: 10 hot water 42 »» 5+ Diazo I. HSOj roughened 0.6 gl. MK aluminum (gives azide of MK) + 2 Gt. Polyvinyl pyrrolidone CH _: 0 inner salt 1: 1.1 (K value 90) ÄGMMÄ / BA / HjO 23 electrolytic 0.6 0.1 Gt. NaNj / 72: 18: 10 hot water 55 Diazo I, HSOf roughened 0.6 Gt. MK aluminum (gives azide of MK) + 2 Gt. Polyvinyl pyrrolidone _ Cf 1: 1.1 (K value 90) electrolytic *) Brush solution like έ 56 Diazo 2, HSOf roughened described below solved, then 0 .. ¹ W Eq. Morpholine added. aluminum The gelatinous precipitate is filtered off with suction, washed with water and poured into 100 Vt. Olyvinylmeihylaceiamid were dissolved (K value 91). ■ ι 1 Gt of the Mixed Committee ÄGMMÄ = Ethyleneglycolniononiethylether; registered, in which 2 Gt. I. BA = butyl acetate

The mixed condensates are produced as follows.

Example 54

In 80 Vt. Methanesulfonic acid (90% Ig) is dissolved by heating 5.68 pbw. 2-Napthol-6-sulfonic acid (Na salt, 87% Ig, component B, No. 13). 2O ⁰ C is then cooled to +, and one carries out, with stirring, first 6.17 Gt. Dlphenylamine-4-dlazonum sulfate (Diazo 1, sulfate) and then 1.2 pbw. Paraformaldehyde. After 24stündlgem stirring at 20 ⁰ C to the deceptive Komlcnsatlonsgemlseh In 1000 Vt. Water a. The pulp is separated in the form of the inner salt, which is sparingly soluble in water. It is filtered off with suction, washed by suspending it several times in water and dried. Yield: 7.1 pbw. The product contains dlazo compound and sulfonic acid bound in a molar ratio of 1: 1. The mixed condensate, which is very sparingly soluble in water (inner salt), can be converted into an azide which is completely soluble in water by treatment with sodium azide, which proves that a real mixed condensate is present. (C 58.2%, N 9.5%, S 6 9% atomic ratio 24: 3: 1.06)

Example 55 %

5.58 Gt. 2-methoxy-naphthalene-6-sulfonic acid (93.3'Wg, component B, no. 23) are available in 80 Vt. on 60 ''

heated methanesulfonic acid (90% Ig) dissolved. 6.17 parts by weight are then dissolved in the cooled solution with stirring. iJ

Dlphenylamine-4-dlazonum sulfate (Diazo 1, sulfate) and then treated with 1.2 pbw. Para- - ") ^ formaldehyde. After 20 hours of condensation at room temperature, π heated to 40" C in 1000 Vt

Poured water and l '/ ₂ hours. Maintained at this temperature. The condensation product is sucked off, §

washed by suspending in water and dried. Yield: 8.2 pbw. The product that is called Inner Salt ■!

contains, according to analysis, dlazo compound and sulfonic acid in a ratio of 1: 1.1 (N 7.8%, S 6.2%, Atomic ratio 3: 1.04). The condensation product, which is practically insoluble in water, can be treated by treatment Convert into a water-soluble azldo compound with aqueous sodium hydroxide solution. This proves that there is a mixed condensate.

To prepare the coating solutions for Examples 54 and 55, il * Dlazo compound is dissolved in water with the amount of sodium given in Table 5 reacted and the reaction mixture to the rest Solvents dissolved polymer added. .v>

Example 56

The Dlazomlsch condensate is produced as in Example 37, but using the component 41 instead of component 40.

Example 57 _

An aqueous solution containing 0.55% is spun onto a sandblasted polyester film. of the mixed condensate described below and 5.5% polyvinyl methyl acetamide (K value 91). To imagewise exposure, the areas not hit by the light are removed with water and after Dry the crosslinked image areas colored with an aqueous crystal violet solution.

The mixed condensate is produced as follows:

In 50 Vt. 86% long phosphoric acid dissolves 6.5 pbw. 3-methoxy-d! Phenylamine-4-dlazonlum-phosphate (Diazo 2, Phosphate) and then contributes 3.9 pbw with vigorous stirring. Hexa-methoxymethyl-melamine (component - »5 Β ,, No. 28) and condensed for 20 hours at room temperature. Previous year

The condensation product is made from the raw condensate as dihydrogen phosphate with 1 mole of phosphoric acid deposited by precipitation with isopropanol.

Yield: 9.1 pbw. (C 32.9%, N 11.6%, P 14.9%) According to analysis, the product contains approximately the elements C and N In a ratio of 10: 3.

Example 58

A waterproof paper carrier with a hydrophilic matt layer made of barite, kaolin and finely divided Silicic acid In hardened polyvinyl alcohol is coated with the following solution through tampons and dried::

2 Gt. of the mixed condensate described below 0.52Vt. 10 η hydrochloric acid

10 Vt. Water 60;

50 Vt. Ethylene glycol monomethyl ether ti

50 Vt. Dimethylformamide "

After normal exposure under a negative, an aqueous solution containing 2.2% fi Na ₂ HPO ₄ - 12 H ₂ O and 2.7% ammonium chloride. A printing form with good inking properties is obtained

happy. S.

The mixed condensate used is produced as follows: * | In 150 Gt. 80% sulfuric acid quickly becomes 3.0 pbw at 80 ° C. 3-methoxy-diphenylamine (component B P

No. 4) and 3.1 Ot. 4-chloro-dlphenylamine (component B, no. 3) gel? · .. As soon as everything is dissolved, it is quickly cooled to + 30 ° C, and 14.7 parts by weight are added to the mixture at this temperature. Dlphenylamine-4-dlazonum sulfate (Diazo I, sulfate) dissolved. A solution of 2.4 pbw is then added at room temperature. Paraformaldehyde In 25 Vt. 80'Wger sulfuric acid is added dropwise slowly with stirring, whereby an increase in temperature above 25 ⁰ C avoided by cooling. After one hour of condensation at 40 ° C., a water-soluble crude condensate is obtained. This is 50 Vt. Methanol diluted, with 2000 Vt. Isopropanol precipitated, the precipitate sucked off, twice with 500 Vt. Washed isopropanol with suspension and finally dried at 40 ° C. in vacuo. Yield: 17.5%. According to analysis, the mixed condensate (sulfate) contains approx. D.26 moles of 3-methoxy-dlphenylamine and approx. 0.08 moles of 4-chloro-dlphenylamine per mole of dlazo compound. (C 50%, N 1196,

I "Cl 0.7%, OCH, 1.9%, S 9.5%, atomic ratio 68: 12.8: 0.32: 1: 4.84)

Example 59

An electrolytically grained aluminum foil is made with a solution of the following composition coated:

1 Gt. of the mixed condensate described below 4 Gt. Polyvinylpyrrolidone (K value 90) 0.1 pbw. Krlstallvloletl (CI. 42555) w 88 Gt. water

12 Gt. Ethanol

If the copy material is exposed under a negative and then developed by rinsing with water, so results in a positive tanning pattern in blue color.

To produce the mixed condensate, proceed as follows: 3.42% by weight. 2-Dlmethylamlno-naphthalln (component B, No. 7) and 6.17 Gt. 95% Dlphenylamine-4-dlazonum sulfate (Diazo 1, sulfate) are in 40 Vt. 90 * iger Methanesulfonic acid dissolved. 1.2 Gt. Paraformaldehyde are slowly added with stirring at room temperature. After condensation in the summer at room temperature, it is diluted with 300Vt. Water and falls that Condensate at 80 ° C by adding 50 Vt. 50% long aqueous Zlnchlorld solution. After cooling to 20 ° C the condensate is separated. In 300 Vt. Dissolved water at 50 ° C, by adding 30 Vt. the above Zinc chloride solution precipitated again and dried after suction. Yield: 9.4 pbw. The mixed condensate According to analysis, contains approximately 0.6 moles of the amine per mole of dazo compound. (N 9.2%, ND 5.1%, atomic ratio 3.61: 2)

35 Example 60

A commercially available paper printing film is coated with the following coating solution using tampons:

0.5 Gt. of the milk condensation described below • »o 50 Vt. Ethylene glycol monomethyl ether

50 Vt. water

After the Koplerschlcht has dried on, the image is exposed under a negative and then with it Water wiped over. A very colorful positive printing form is obtained.

■ »5 The mixed condensate used is produced as follows:

In a mixture of 100 Vt. 90% long sulfuric acid and 40 Vt. 96% long sulfuric acid becomes at 40 ° C 13.8Gt. 4-Hydroxy-benzoic acid (component B, no. 12) dissolved. One cools rapidly to room temperature, dissolves 30Gt. 97.6% pure diphenylamine-4-dlazonium sulphate (Diazo 1, sulphate) and cools down further to + 5 ° C to + 10 ° C. At the same temperature a solution of 6Gt. Paraformaldehyde in 20Vt. 90% long sulfuric acid dripped in. It is stirred for a further 30 minutes at the same temperature and heated to 1000 Vt. Poured ice water. That precipitated product is suctioned off, in 500 Vt. Suspended water, filtered off with suction and dried. Yield: 46.6 Gt. According to analysis, 4-hydroxybenzoic acid and dlazo compound are approximately in the molar ratio in the condensate 1: 1 built-in. (C 49.7%, N 8.5%, ND 5.6%. S 6.9%, atomic ratio C: N: ND: S about 20.7: 3: 2: 1.08)

Example 61

The procedure is as in Example 60, but a coating solution of the following composition is used for coating:

2 Gt. of the mixed condensate described below 0.75 Gt. 86% lge phosphoric acid 100 Vi. water

65 The processing is carried out in the same way as in example 60 with a very similar result. To produce the mixed condensate, proceed as follows:

In 100 Vt. 80% sulfuric acid is 15.42%. Dissolved diphenylamine 4-dlazonium sulfate (Diazo I, sulfate). With thorough stirring, 8.83 pbw. Dimethylol-succindiamide (component Bi, No. 26, finely powdered) in

46

JLKJ Z, * t itt

gen, the temperature being kept at +25 "C by cooling. Condensation is carried out for 15 minutes per hour at room temperature, dissolves the raw condensate in 500 Vt. Water and separates the condensate by adding 80 Vt. 5O '\. Iger Zinc chloride solution. The precipitate is separated off at 50 ° C in 500Vt. Dissolve water and add 50Vt. 50% zinc chloride solution precipitated again, filtered off with suction and dried in vacuo. Yield: 18.6 pbw. (C 40.8%, N 11.6%, ND 5.35%, atomic ratio 17.8: 4.35: 2) The analysis suggests a build-up of a second component, but a certain saponification of carbonamide groups appears to have taken place.

Example 62

This example shows the superiority of certain milk condensates over known dlazodophenyls > amin-formaldehyde condensates in the hydrophilic hardening of water-soluble colloids. Hydrophilic hardened Colloids are used for a particular type of positive working pre-insulated printing plate Meaning (see. US-PS 30 85 008).

With this type of plate, a mixture of a hydrophilic one is placed on an oleophilic support surface Polymers and a Dlazo blending applied. In the case of a smaller exposure under a positive, the o Colloid cross-links and should grow on the oleophilic carrier. Then the non-exposed layer is applied developed away and exposed at these points the oleophilic carrier as the color-transferring image area. It the result is a positive printing form.

Since the light decomposition products of known formaldehyde condensate are oleophll, the proportion of Diazokondensai must not be too high, on the other hand, the layer must be well vcrncui possible to the attack - to withstand ^r 'in the printing process better, which in turn occurs when the proportion of Dlazo blending is high.

This example shows in comparison

a) a with a prepared according to Example 1 of DE-PS 11 38 399 chloride of the formaldehyde condensate des Dlphenylamln ^ -diazoniumchlürldes,

b) one with a chloride of a mixed condensate of diphenylamine-4-dlazonium salt and methylol urea (Production see below)

manufactured printing plate of this type.

A according to DE-PS 11 60 733, Example 1, manufactured vorscnslblüslerie planographic printing plate is z. B. with the light of an arc lamp completely blown out. The plate is then rinsed with water and dried. the The plate is halved and one half of the plate is coated with one of the following solutions 1 and 2 and the coating dried on.

1. 0.125 Gt. of the condensate mentioned under a) 0.38 Gt. Polyacrylamide

100 Vt. water

2. 0.125 Gt. of the flour condensate mentioned under b)

0.38 Gt. Polyacrylamide J0

100 Vl. water

After imagewise exposure under a positive is developed by wiping over with water and with colored in bold color.

While in case 1 a positive printing form with a very strong toning in the little night blooms is obtained one with the solution 2 one, apart from small Beschlchtungsfchler. flawless positive planographic printing form, whose non-image areas (hardened hydrophilic colloid) do not take on color.

The mixed condensate used is produced as follows:

In 50Vt. 36.5% long aqueous hydrochloric acid are 23.2%. Dlphenylamine-4-dlazonlumchloild (Diazo I, chloride) solved. Then carry 12Gl with vigorous stirring. finely powdered dimethylolurea (component Bi, No. 29) and stirred for 3 hours at room temperature and then for 1 hour at 40 °. After standing overnight (refrigerator) with 80Vt. Methanol and diluted in 1200Vt. Stir in isopropanol. the Precipitation is sucked off, quickly twice with 400 Vt each. Washed isopropanol and dried in vacuo at 40 ° C. Yield 15 pbw (Chloride). A yellow, water-soluble powder is obtained which, according to analysis, has per diazo group contains about 0.9 molecules bound urea. (N 19.6%, ND 8.2%, Cl 10.8%, atomic ratio 4.8: 2: 1.04)

Example 63

The aluminum support used in Example 40 is coated with a coating solution as follows Composition: ω

1 Gt. of the mixed condensate given below

2 Vt. 1 η hydrochloric acid

0.4 Gt. Diazo condensate according to DE-PS 11 38 401, Example 1, adjusted to 2.8 molecules of phosphoric acid per diazo group

1 Gt. Polyvinyl acetate with a minimum molecular weight of 110,000 (determined by light scattering) 4 pbw. water
77 Gt. Ethylene glycol monomethyl ether

47

19 Gt. BiUylacetat

A very light-sensitive copying material is obtained by drying the coating. The processing to: Printing form can be made with the developer mentioned under Example 40, whereby a Post-development with the developers mentioned in Example 36 can be beneficial. The mixed condensate is produced as follows:

7.33 Gt. Dlphenylamine-4-dlazonum sulphate are used in 100 Vt. 90% longer methanesulfonic acid dissolved. Mail now resolves 2.1 Gt. Diphenylene oxide (component B. No. 24) In 35 Vt. Glacial acetic acid, further 3.75 gt. 30% aqueous formaldehyde solution In 5 Vt. Glacial acetic acid, combine the two acetic acid solutions and drop the mixture while stirring. In a hurry i "initially prepared diazo solution. The mixture is stirred at 40" C for 4 hours. After standing for 36 hours at room temperature the raw condensate, which is soluble in water without residue, is dissolved in 1250 Vt. Stir in isopropanol. The resulting suspension is stirred at 40 ° C. until the precipitate settles out when the stirrer is switched off. One suck; off, wash twice while suspending with 250 Vt. Isopropanol and dries in vacuo. Yield: 5.9Gt. According to analysis, the mixed condensate contains about 1 mol of bound phenylene oxide per mol of oleo compound. (C 60.8%, N 8.1%, S 6.1%, atomic ratio 26.3: 3: 1)

Example 64

A Trlmetallplatte (Al-Cu-Cr) is poured with a Beschlchtungslösung following composition exceeds ^Jn, the excess of the solution is drained ynrl * the plate dried.

2 Gt. of the chloride of the mixed condensate described below

1 Gt. Polyvinyl alcohol (residual acetyl content 12%. Viscosity of the 4% aqueous solution 6.5 to 8.8

mPa s at 20 ° C)
25 50 Vt. water

After imagewise exposure under a positive, the developers described in Example 36 are used developed and then with an aqueous solution containing 30% calcium chloride, 20% Zlnkchlorld, about 1.5 to 3% ammonium chloride, tartaric acid and concentrated hydrochloric acid contains the chromium as chromium etch Copy layer exposed pirtles etched away down to the copper. The coating is removed by treating with a paste consisting of whiting chalk and dimethylformamide. The result is a positive multi-metal printing form, which allows a very large print run.

To prepare the mixed diazo condensate, the procedure is similar to that of Example 37, but the following are used Reaction partners and working conditions at:

32.3 Gt. S-melhoxy-dlphenylamine ^ -dlazonlumulfat (Diazo 2, sulfate) 170 pbw. 86% lge phosphoric acid
64.5 Gt. Meihoxymethyldlphenylälher from CMDPO-32 (component Bi. No. 48, see below)

• ω Condensation was carried out at 40 ° C. for _{2 hours.} Dissolved in water, filtered clear, precipitated in hydrochloric acid, dissolved again and precipitated again with hydrochloric acid. Yield: 44 pbw

The chloromethylated phenyl ether CMDPO-32 has a ClijCI Substltutlonsgrad of 2.8 and consists of the following components:

45 2,4'-Di-chloromethyl-dlphenylether 1.9%

4,4'-Dl-chloromethyl-dlphenylether 8.6%

2,2 ', 4'-Trl-chloromethyl-diphynyl ether 17%

2.4,4'-trichloromethyl-dlpheny! Ether 72 %

2,2 ', 4,4'-tetra-chloromethyl-dlphenyl ether less than 2%

The ether mixture obtained by replacing the halogen atoms with methoxy groups possessed a Methoxy content of 28.9%. It was used to prepare the condensation product, its elemental analysis was as follows:

(C 67.5%, N 4.4%, Cl total 4.3%, Cl ionogenic 3.8%, OCH ₁ 12.7%, atomic ratio 53.6: 3: 1.16: 1.03: 3.92) The The analysis result shows that this mixed condensate still contains considerable amounts of reactive methoxymethyl groups.

A copier material that can also be used with good success is obtained if the same carrier is used the following coating solution coats and the coating dries.

w 1 Gt. of the mixed condensate described in Example 37

2 Gt. of the polyvinyl alcohol used in the present example also above 50 Vt. water

The development after moderate exposure is carried out with the water shower. The further embedding for multi-metal printing is done as indicated at the beginning of this example.

Instead of the Ai-Cu-Cr carrier, a brass filament can also be used, which is provided with a thin Chromium layer is coated.

48

Example 65

A copper plate is rinsed with a 1 to 2% iron-HI-chloride solution for a few seconds Rinsed off water, then cleaned with whiting chalk, rinsed off again and dried. The plate is .with a solution of

8 Gt. of the mixed condensate described below in 100 Vt. of a mixture of 8 Vt. Ethylene glycol monomethyl ether and 2 Vt. Butyl acetate

poured over it, and the coating is dried with a hot air blower.

After imagewise exposure under a grid positive Qberwischi one for a few seconds with a 10% Solution of n-propanol in water and finally developed with the developer I given in Example 36. until the unexposed areas are free of copy layer.

The dry plate is then etched in the usual way with 40% iron III-Chlorld solution. The result is a autotypical gravure form.

To produce the mixed condensate, the same procedure as in Example 64 is followed, but the following amounts of substance are used and conditions.

323 Gt. Diazo 2, sulfate

17G Gt. 86% phosphoric acid

32.2 Gt. Component Bi, No. 48

It is _{condensed for 4 1/2} hours at 40 ° C., the condensation product is separated out from an aqueous solution with saline solution, redissolved and precipitated again with saline solution. The final separation takes place as Mesltylenesulfonat. Yield 55.7 pbw. (C 66.7%, N 5.8%, S 4.7%, OCH, 7.8%, atomic ratio 40.2: 3: 1.06: 1.82)

The analysis result shows that in this condensate there are still significant amounts of reactive methane : ymethyl groups are included.

Examples 66 to 78 -W

These examples show the suitability of a number of mixed condensates made from various components and in different forms of deposition (light-sensitive sulfonic acids and multifunctional sulfonic acids) for light-sensitive copier layers for the photomechanical production of planographic printing forms.

It is surprising that the precipitate used in Examples 71 and 72 from the flour condensate, which is polyfunctional, and the divalent sulfonic acids are readily soluble in organic solvents.

Data on the mixed condensates used, the coating solutions and the development can be found in Table 6.

In some cases, phosphoric acid has been added to the coating solutions. The addition of phosphoric acid, e.g. B. already 0.1 to 0.3 moles per mole of dlazo groups, influences the bearing of the coated material and whose developable value is cheap.

After imagewise exposure under a negative is immediately a generally blue-green one. In case of Example 71 more brown image clearly visible.

Development can be carried out with one of the developers I or U given in Example 36.

Obtained after inking with a greasy color printing forms which * s provide a large number of flawless prints. The print run can be significantly increased if the well developed printing form is reinforced with one of the usual varnishes.

The printing plates coated according to the instructions in Examples 66 to 73 are more light-sensitive than those using the formaldehyde condensate of the Dlazo compound according to DE-PS 1138 401, Example 1. Snid has been made. The greatest increase in photosensitivity is found in Examples 70, 75 and so on 76, whereby the materials of Examples 75 and especially 76 because of the easier manufacturability and the better Solubility of the products are preferred. Also the shelf life of the last two printing plates mentioned Is remarkably good.

In Examples 66 to 76, the substrate was electrolytically roughened, then anodized and finally aluminum foil treated with polyvinylphosphonic acid, In the examples! 77 and 78 by metal brushes Use roughened aluminum treated with polyvinylphosphonic acid.

In addition to the carriers used here, a number of carriers can be used for the> > Wlpe on «processes with the well-known Dlazo resins are recommended and are on the market, also in connection with the copying layers according to the invention are used.

49

Tabel j. 69 6th Mixed condensal (MK) Compo Secluded as Ratio Brush solution Acid addition solvent! developer KJ example Diazo compound nent B ₁ AN ₂ X: B ₁ % MK (Volume parts) O A - N; X in the MK approx. KJ 35 Naphthalene-1-SO.r 1: 0.57 - ethylene glycol 4 *. 70 Diazo 2nd HSO _4th 2 monomethyl ether / I or II KJ 66 Butyl acetate 8: 2 35 PF ₁ , " 1: 0.42 - ethylene glycol 71 Diazo 2, HSO ₄ " 2 monomethyl ether / I or II 67 Dimethylformamide 6: 4 36 Naphthalene-1-SO.f 1: 0.57 - ethylene glycol 72 Diazo 2, HSO ₄ " 2 monomethyl ether / I or II 68 Butyl acetate 8: 2 36 PF ₆ " 1 x 0.31 - ethylene glycol Diazo 2. HSO ₄ " 2 monomethyl ether / I or II Butyl acetal . 8: 2 43 Cf 1: 0.63 - ethylene glycol Diazo 2. H; PO ₄ " 2 monomethyl ether / I or II Butyl acetate 8: 2 36 Diazidostilbene 1: 1 0.06 pbw, 86% ethylene glycol Diazo 2, HSO ₄ " disulfonate 2 Phosphoric acid / weight MK monomethyl ether / I or II Butyl acetate 8: 2 36 Di-tert-butyl 1: 0.75 0.036 Gt. 86% ethylene glycol Diazo 2, HSO ₄ " napiuhalin-di-SOj 2 Phosphoric acid / weight MK monomethyl ether / I or II Butyl acetate 8: 2

continuation Diazo compound Compo Secluded as relationship Brush solution Acid addition solvent developer to A-NjX nent Bi A-NjX: B, % MK (Volume parts) O Example mixed condensate (MK) in the MK approx. Diazo 2, HSO ₄ " 36 Naphthalene-2-SO3 " 1: 0.96 0.031 Gt. 86% eat Ethylene glycol IO 2 Phosphoric acid / weight MK monomethyl ether / I or II -Ρ » Butyl acetate 73 8: 2 Diazo 2, H ₂ PO ₄ " 37 a ' 1: 0.77 0.22 Gt. 86% Ethylene glycol 2 Phosphoric acid / weight MK monomethyl ether / 1 or II Dimethylformamide 74 6: 4 Diazo 2, HSO ₄ " 41 2-diazo-1-naphthol-5-SOj 1: 1.1 0.035 Gt, 86% ii ', e Ethylene glycol 2 Phosphoric acid / weight MK monomethyl ether / I or II Dimethylformamide 75 6: 4 Diazo 2, HSO ₄ " 41 Mesitylene SOj " 1: 1 - Ethylene glycol Naphthalene-2-SOj " 1: 0.68 mouomethylätlier / I or Il 2 Butyl acetate ~ 76 8: 2 Diazo 2. Η _: ΡθΓ 43 Cf 1: 0.63 0.355 Gt, p-toluene Ethylene glycol 0.4 sulfonic acid H: O / monomethyl ether / Il Gt. MK ButylacetHt 77 8: 2 Diazo 2, H _: PO ₄ " 37 Cl " 1: 0.77 0.425 Gt. p-toluene Ethylene glycol 0.4 sulfonic acid · HjO / monomethyl ether / II Gt. MK Butyl case 78 8: 2

'j; The diazo compounds used in Examples 66 to 76 are prepared as follows:

fi Examples 66 and

-; > The condensation is carried out analogously to Example 37, but the following conditions and substances are used applied:

^ 120 Gt. 86% Ige phosphoric acid

32? Gt. Diazo 2, sulfate; ίο 8.3 Gt. l ^ -DlmethyM.o-dlmelhylol-benzcl (component B ₁ , no. 35)

Ec is condensed at 40 ° C. for 20 hours. Half of the mixture (Example 66) is dissolved in water, the \: precipitated \ condensate with brine and the precipitate was dissolved in water and a salt of naphthalene-1-

': sulfonic acid like. Yield: 11.5%. (C 65.5%, N 8.0%, S 6.1%, atomic ratio 28.7: 3: 1).

.-Τ is The average molecular weight of the dye with phenylmethylpyrazolone is 1256.

:: The other half (Example 67) of the crude condensation mixture is dissolved in water and treated with hexafluoro-

: phosphoric acid precipitates the corresponding hexafluorophosphate.

Yield: 21.2 pbw. (C 45.4%, N 9.2%. Atomic ratio 17.2: 3). The precipitation still contains some uncondensed diazo compound.
; .-. ¹⁰
V. Examples 68 and 69

; The procedure is as in Examples 66 and 67, but the following substances and conditions are used:

25 120 Gt. 86% phosphoric acid

32.3 Gt. Diazo 2, sulfate

11.1 Gt. 4,6-diisopropyl-1,3-dlmethylol-benzene (component Bi, no. 36)

It is condensed at 40 ° C for 20 hours. Half of the mixture (Example 68) is dissolved in water that 30 Condensate precipitated with saline solution, the precipitation dissolved again in water and as the salt of naphthalene-1-sulfonic acid pleases. Yield: 13.3 pbw. (C 66.3%, N 7.5%, S 5.6%, atomic ratio 31: 3: 0.98). Average molecular weight of pyrazolone dye 1299.

The second half of the mixture (Example 69) is dissolved in water, and the hexafluorophosphate is precipitated from this solution with hexafluorophosphoric acid.
35 Yield: 11.1 pbw. (C 52.9%, N 10.7%, atomic ratio 17.3: 3).
The product still contains uncondensed diazo compound.

Example 70
• to Man proceeds in a similar way to Example 36. However, the following conditions or substances are used:

200 Vt. 86% lge phosphoric acid

3.23 Gt. Diazo 2, phosphate

1.33 Gt. 9,10-Bls-melhoxymethyl-anthracene (component B ₁ , no. 43)

45 in 20 Vt. Glacial acetic acid.

The second component is dissolved in boiling glacial acetic acid and poured into the dlazo solution. The condensation takes 20 hours at 40 "C. The condensation product is deposited as chloride.
Yield: 2.8 pbw (C 51.1%, N 7.8 ?, atomic ratio 23: 3)

Examples 71 and

To prepare the condensation product, the procedure is similar to that in Example 25, but the following conditions or substances are used:

240 Gt. 86% lge phosphoric acid 64.6 pbw. Diazo 2, sulfate

44.4 Eq. Component Bi, No. 36 (cf. Examples 68 to 69).

It is condensed at 40 ° C for 20 hours.

The crude condensation mixture is dissolved in water and the solution is divided in half.
From the first half (Example 71), the condensate is first precipitated with hydrochloric acid as the chloride and then as the salt of 4,4'-dlazldo-styrene sulfonic acid.

Yield: 41.9 pbw. (C 63.7%, N 12.9%, S 4.8%, atomic ratio 70.6: 12.3: "!).

<^ From the second half of the solution (Example 72) the condensate is obtained directly as the salt of 2,6-Dl-tert.-butylnaphthalln-dlsulfonsäuic pcfälll.

Yield: 38.3 gl. (C 68, K. N 7.7 * ,, S 4.9%, atomic ratio 31: 3: 0.835).

52

Example 73

The condensation is carried out as in Examples 71 and 72. However, the condensate is separated off first with hydrochloric acid and finally with naphthalene-2-sulfonic acid. (C 68.3%, N 6.6%. S 4.9%. Atomic ratio 36.2: 3: 0.98)> k]

K Example 74 > \\

The procedure is similar to Example 18, but the following substances h / .w. Conditions applied: | j

4.85 Gt. Diazo 2, phosphate · |

15 Vt. Methanesulfonic acid 90% lg yyyy

2.04 Gt. l.S-Dl-acetoxymethyl-naphthalln (component Bi, No. 37) |

The condensation takes place in 2 hours at room temperature. The condensation product is deposited as chloride.
Yield: 3.2 pbw. (C 64.0%, N 9.4%, atomic ratio 23.8: 3)

Example 75: o Si

The condensate described in Example 40 is deposited as a salt of 2-dlazo-1-naphthol-5-sulfonic acid and dried over phosphorus oxide to constant weight.

Example 76

The I: 1 condensate corresponds to that used in Example 40 fc for the preparation of the Azo dye is used.

The further condensate, which 3-methoxy-dlphenylamine-4-dlazonum salt and second component in the ratio 3 « nls of about 1: 0.67 is prepared analogously to the information in Example 40 according to the following data:

120 Gt. 86% phosphoric acid
32.3 Gt. Diazo 2, sulfate
12.9 Gt. Component Bi, No. 41 (98-DIs 99% lg) 35

It will be 2! SiUftdcn condenses at 40 ° C and the product: iweima! precipitated as chloride with hydrochloric acid. Finally it is deposited as the salt of naphthalene-2-sulfonic acid.

Yield: 35 pbw (C 67.0%, N 7.2%, S 5.6%, P 0.18%, Cl 0.21%. Atomic ratio C: N: S = 32.6: 3: 1) The average molecular weight of the azo dye with phenylmethylpyrazolone is 1455. w

A fractionation attempt by fractional detachment of a film of the dye from aluminum foil results the following values:

hlnrnlnrm Melh: innl l ^; raklion N middle

fraction
No. chloroform
(ecm) Methanol
(ecm) l 'instruction
lot
(mg) N
'«Ii middle
Molecular weight 1 150 1.5 - - 2 60 90 90.9 13.5 874 3 67.5 82.5 217.7 13.6 1097 4th 75 75 274.1 13.2 1261 5 82.5 67.5 232 12.6 1779 6th 90 60 204.2 12.2 2475 7th 150 143.3 11.5 3995

Example 77,

The condensate described in Example 70 is used.

Example 78; "

The condensate described in Example 74 is used.

53 ι

Example 79

The carrier used in Examples I to 35 is ^{coated with a I 1} A ₁ IgCn wMUrlgen solution of the dlazomal condensate described below, to which - based on the weight of the mixed condensate - 50% by weight 85% phosphoric acid has been added. (The emptying solution is somewhat cloudy.) After drying, the material is exposed to light and then developed, as in Examples 1 to 35, into a printing form that accepts color well.
Γ The mixed condensate is produced as follows:

4, ü Gt. Dlphenylamine-4-dlazonum sulfate and 2.2 pbw. 3-aminopyrene are heated gently in 30 Vt.

90% longer methanesulfonic acid dissolved. After cooling to room temperature, 0.75 pbw is added with stirring. Paraformaldehyde to. After stirring for a further 3½ minutes, the raw condensate is fed into without delay aqueous hydrochloric acid heated to 90 ° C. (200 pbv. Water and 100 pbv. 18% aqueous hydrochloric acid). After a quick

Cooling The precipitate is filtered off with suction in an ice bath, washed with 0.5 η hydrochloric acid and dried. Yield:

4.8 Gt. According to the analysis, the product has an atomic ratio of C: N = 31.4: 4, while the dlazo homocondensate a ratio of 17.3: 4 and the amine homocondensate has a ratio of 68: 4 (C 65.1%, N

9.7%).

Example 80

v> An electrolytically roughened aluminum support is coated with the following coating solution and the coating is dried on:

5.0 Gt. Polyvinyl alcohol (degree of solubilization: 88%; viscosity of the 4% aqueous solution at 2O ⁰ C:

6.5 to 8.8 mPas)

25 0.5 Gt. of the Dlazoml condensate described below

94.5 Gt. water

After moderate exposure, development is carried out by rinsing with water. Coloring with aqueous crystal violet solution (CI 42555) gives a blue tanning pattern.
-W A mechanically roughened polyethylene terephthalate film can also be used as a carrier.

The mixed condensate is produced as follows:

8.5 Gt. 2-Phenyl-amlno-pyrldln are sold in 50 Vt. 80 liters of sulfuric acid dissolved at a temperature not exceeding 35 ° C. The solution is cooled to 15 to 20 ⁰ C and a mixture of 15 pbw for 10 minutes. 97.6% total dlphenyiamine-4-dlazonium sulfate and 3,000. Paraformaldehyde stirred in. The mixture is stirred for a further 3-5 hours at room temperature and left to stand for 14 hours. To separate off the mixed condensate, the mixture is diluted with 70 Vt while cooling. Methanol and stir in 700 Vt. Isopropanol. The product is filtered off with suction, suspended and twice 500 pbv. ! sopropano! washed. Yield: 25.6 pbw, as sulfate. According to analysis, the product contains approximately 0.8 moles of twofold components per mole of dlazo compound. (N 10.4%, ND 4.6%, atomic ratio 4.52: 2)

Example 81

This example shows that the oleophilic of the exposure products of the novel diazo condensates also is still clearly noticeable under extreme conditions.

■ 15 A superficially soaped cellulose acetate fill is mixed with a solution of 2 pbw. of the welter described below Raw condensate in 98 Gt. Water is coated with tampons and the coating is dried on. Although the solution is very dilute and contains around 75 molecules of phosphoric acid per dlazo group, the Image areas of the image-wise exposed film remove the water when wiped over with water, but they become greasy Color on.

For comparison, a plate in the same catfish is coated with a solution that contains one of the dlazo groups the above coating solution contains an amount of D'azo groups equivalent to that, however, as a diazo compound the formaldehyde condensate produced in US-PS 34 06 159, Example 1, without the co-reaction of a second component Was used. The relation of Dlazc groups to phosphoric acid is on the same Value as set in the above Mlschkondensallonsgemlsch.

After image-wise exposure, the unbleached and exposed areas of the layer are equally hydrophilic. the Bleaching products cannot be colored with bold paint. The mixed diazo condensate is produced as follows:

In 33.8 Gt. 86% phosphoric acid is 1.29%. S-methoxy-dlphenylamlrnl-dlazonlumphosphhal dissolved. at At room temperature you add 0.36 pbw. Paraformaldehyde and immediately thereafter 0.68 pbw. Thlophen under violent

w stirring too. The mixture is stirred for 3 hours at room temperature and left to stand overnight. Except for a minor one Resin separation on the stirrer, the raw condensate is clear and clearly soluble in water. The raw condensate is used in this form to prepare the coating solution. n,

• '• 5 Example 82

This example shows that mixed condensates which contain only a small amount of diazo compound can still be used Copy materials result.

An electrolytically roughened aluminum foil is coated with a 2% solution of a mill condensate (which, according to analysis for a 3-methoxy-4-dlazo-dlphenylamine cover, contained about 18 p-Krcsolelnhelt) In Ethylene glycol monomethyl ether coated and the coating dried on.

After imagewise exposure under a negative, it is rinsed with acetone for development, dried, wiped over with water and colored with felter paint.

A slightly toning positive printing form is obtained, which can be washed out with a solution of 75 Vt. Water, 35 Vt. n-propanol and 2 pbw. NaH ₁ PO ₄ · 2HjO can be purified.

If, under the same conditions, a condensate consisting only of p-cresol helices is produced and set the amount of S-Methoxydlphenylamln ^ -dlazonlumchlorld corresponding to the amount of dlazo compound incorporated subsequently, a copy layer is obtained with this mixture and after imagewise exposure and development with acetone also a toning positive printing form. However, this printing form is used in Try to clean them by wiping them with the above solution, completely destroyed.

Even if the subsequent addition of Dlazo connection is increased tenfold, the result will not be better achieved.

For the production of the mixed condensate 0.323Gt. Dlazo-2, sulfate, in 100 Vt. Dissolved 86% phosphoric acid, and a solution of 3.36% is poured into this solution while stirring vigorously. 2,6-dimethylol-4-methylphenol In 20Vt. warm methanol. At the moment of mixing, a clear solution is obtained which, however, quickly becomes cloudy with the separation of the condensate. After stirring for an hour and standing overnight, 400 Vt. Water and diluted with 50Vt. saturated saline solution added. The precipitation ^w! Sucked rd, washed neutral with water and dried. Yield 2.8 pbw (C 71.0%, N 1.4%, atomic ratio 177: 3) Analysis of the homocondensate prepared under the same conditions from 2,6-dimethylol-p-cresol: (C 71.656, H 7.1%). The analysis suggests a benzyl ether-type linkage between the building blocks.

Examples 83 to 92

Examples 83 to 92 again show the good oleophilicity of the puffing-out products of a number of Dlazoml condensates on superficially silted cellulose acetate. The resulting from the condensation Mixtures are used directly for coating after dilution to show that even without separation the high amounts of acid the effect according to the invention is already effective. Of course they are Results are even better if not such high amounts of acid are added. For practical purposes one will Prefer acid additions of less than 3 moles per mole of dlazo groups on this carrier.

Details about the condensation and the dilution solutions are given in Table 7.

Examples 86, 88, 90, 91 and 92 gave the best results. In examples 84 and 85 the effects are naturally weakest because of the high acid content.

For comparison, a condensation product of dlazo-2, chloride and formaldehyde in 2.8 basic moles Phosphoric acid prepared analogously to Example 1 of US-PS 34 06 159 and the phosphoric acid level to 15 basic mol set. With Issiger and with the above aqueous solution this mixture was saponified on the surface Cellulose acetate film gives virtually no color acceptance after imagewise exposure and development with water In the image areas.

Table 7 Mixed condensates
Diazo compound
A - N ₃ X Compo
nent
B, relationship
A - N; X TO
B ₁ in MK approx. mole
phosphorus
acid
per mole
Oiii / .o-
groups approx. Brush solution
percent
sentence, at
Raw
condensate solvent Ent
winder example Diazo-2-sulfate 54 1: 1 15th 1 HjO H _: O 83 Diazo-2-sulfal 49 1: 1 150 10 H ₂ O / melhanol
1: 1 H ₂ O 84 Diazo-2-sulfate 50 1: 1 130 10 H ₂ O / methanol
1: 1 H ₂ O 85 Diazo-2-sulfate 51 1: 1 15th 2 H ₂ O H ₂ O 86 Diazo-2-sulfate 57 1: 1 15th 2 H ₂ O H ₂ O 87 Diazo-2-sulfate 55 1: U 20th 2 H ₂ O H ₂ O 88 Diazo-2-sulfate 56 1: 1 20th 2.5 H ₂ O H ₂ O 89 Diazo-2-sulfate 52 1: 1 32 4th H ₂ O H ₂ O 90 Diazo-2-sulfate 53 1 : \ 80 2 and 10 H ₂ O H ₂ O 91 Diazo-2-sulfate 58 1: 1 42 • 2 H ₂ O H ₂ O 92

55

The mixed condensates are produced as follows:

Example 83

Production of the component Bi 12.4Gt. 4,4'-Dimethyl-diphenyl ether are In 27 Vt. Glacial acetic acid dissolved, one sets 5.7% with stirring. Paraformaldehyde, then 28 pbw 63% aqueous hydrobromic acid and finally 16.5%. 95% added sulfuric acid. After two hours of warming to 90 to 95 ^° C., it is left to cool down overnight.

The crystals contained in the mixture are filtered off with suction, washed with water and without intermediate dry I " The solution was crystallized from acetone.

Yield 14.75 parts by weight, melting point 109 to! 10 ° C.

The compound is dissolved in benzene and registered in boiling methanolic sodium hydroxide solution (large excess of NaOH). After refluxing for 2 hours, water is added, the benzene phase is separated off, washed, dried and evaporated.
It was 9.2 Gt. obtained from an oily substance (component B ₁ , No. 54 (OCHj: 21.7%)

4.85Gt. Dlazo-2, sulphate are available in 15Vt. 86% lger phosphoric acid dissolved and 4.3 pbw with stirring. the component Bi, No. 54 obtained above was added. A clear, homogeneous reaction mixture is obtained. After 5 hours of condensation at 40 ° C., it is dissolved in water and the condensation product is precipitated as chloride by adding aqueous sodium chloride solution.
2 "yield 6.9% by weight (C 65%, N 7.4%, atomic ratio C: N = 30.8: 3)

Example 84

Component Bi, no. 49, is made from p-hydroxy-benzaldehyde-potassium and 2,2'-dichlorodethyl ether (»macro- -5 molecular chemistry ", 17, 156 (1955 to 1956) and subsequent reduction with sodium borohydride in water-methanol obtain.

To produce the condensate one dissolves 1.62Gt. Dlazo-2, sulfate In 50 Vt. 86% lger phosphoric acid and stir a resolution of 1.6Gt. Component Bi, No. 49, In 5 Vt. almost simmering glacial acetic acid. After 5 hours Condensation at 40 ° C and standing overnight is the raw condensate for the preparation of the coating solution jo used.

Example 85

The component Bi, no. 50, is analogous to component B ,, no. 49, from p-hydroxy-benzaldehyde-Kalum and 1,3-Dlbromopropane and subsequent reduction of the Dlaldehyde to Dlalkoho! obtained with sodium borohydride.

For the production of the condensation product 0.213Gt. Dlazo-2, sulfate In 1.5Vt. 93% long phosphoric acid dissolved and a hot solution of 0.19Gl. Component Bi, No. 50, In 1 Vt. Glacial acetic acid mixed in. To Addition of 3.5 Vt. 93 ft.iger phosphoric acid is kept at 40 ° C. for 5 hours. The raw Hare condensate becomes Used to prepare the coating solution.

Examples 86 and 87

To produce component Bi, No. 51, diphenylene oxide (100 parts by weight) is added analogously to Example 83 in a mixture of 300 parts by weight. Glacial acetic acid, 54 Gt. Paraformaldehyde, 500 pbw 63% hydrobromic acid and 294 parts by weight 96% sulfuric acid at 75 ⁰ C brommethyllert and the reaction product from acetone umkrlstalllslert (BIsbrommeihyl-diphenylenoxld [calculated: C 47.5%, Br 45.3%; found: C 47.7%, Br 46.2%]) and Reacted with excess sodium hydroxide solution in methanol.

For the production of the condensation product 16.2 wt. Dlazo-2, sulfate In 50 Vt. 86% long phosphoric acid solved and 12.8 Gt. Component Bi, No. 51, heated to 35 ° C. and added dropwise.

The condensation takes place for 5 hours at 40 ° C. The clear raw condensate is used directly for the experiment. Of the The remainder of the mixture (deducted: 0.2 pt.) Is dissolved in water and the reaction product from this solution precipitated by saline solution.

Yield: 22.6 pbw. (C 65.7%, N 8.2%, atomic ratio 28: 3)

The preparation of component Bi, No. 57, and from this the condensation product used in Example 87 takes place analogously to Example 86. However, dibenzothlophen is used as the starting material.

Examples 88 to 89

For the preparation of component Bi, No. 55, according to "Lleblg's Annalen der Chemie", 350, p. 89 (1906), thymylphenyl ether prepared analogously to Example 83 is _{bromomethylated for 3 1/2} hours at 90 to 95 ° C. and the reaction product without further Purification with sodium hydroxide solution in methanol reacted. The reaction product, a viscous oil, has an OCHj content of 18.6%.

<>> To produce the condensate, 4.85 Gt. Dlazo-2. Sulphate In 20 Vt. 86% tger phosphoric acid dissolved. 6.0 Gt. of component B ,. No. 55, added dropwise and condensed at 40 ° C. for 4 hours.

The crude condensate obtained in this way (1 part removed) was used to produce the coating solution. Of the The remainder is dissolved in water and the condensation product is precipitated as chloride with saline.

Yield 9 pbw (C 66.9%, N 6.7 *, atomic ratio 35: 3)

The condensate door example 89 is produced analogously to example 88; as starting material for production the component Bi, no. 56, however, according to »J. At the. Chem. Soc. 61, 2702 (1939) manufactured 3-bromo-4-meihoxy-dlphenyl ether used.

Example 90

To produce the component Bi. No. 52, diphenylmeihan is analogous to Example 83 for 5 hours at 90 to 95 ° C bromomethyllert and the pure 4,4'-Bls-bromomethyWiphenylmethan obtained by Umkrtstalllsatlon from benzene (Melting point 153 to 154 ° C) reacted with sodium hydroxide in methanol.

4.85 Gt. Dlazo-2, sulfate In 15 Vt. 86% phosphoric acid dissolved and 3.85Gt. Component Bi, No. 52, was added dropwise. After adding 15Vt. 93% longer phosphoric acid is 10 hours condensed at 40 ° C.

2 Gt. of the raw condensate are used for the preparation of the coating solution, the rest is used in Dissolved water and the condensate precipitated as chloride with aqueous hydrochloric acid, separated off and dried i> (C 68.6 «, N 8.096, atomic ratio 30: 3)

Example 91

To produce component B ₁ , no. 53, diphenyl is bromomethyilerted for 5 hours at 90 to 92 ° C. as in Example 83 and the portion of the reaction product which is sparingly soluble in acetone is reacted with sodium hydroxide and methanol (OCH ₁ : 23.8%).

To produce the condensate you dissolve 6.4 pbw. Dtazo-2, sulfate In 50 Vt. 86% long phosphoric acid, dissolves another 4.8 pbw Component Bi, No. 53, In Vt. warm the methanol and add this solution to the dlazo solution. After 2 hours of heating to 40 ° C, 50Vt. 93% longer phosphoric acid was added. A total of 12 ^l / _l hour at 40 ° C. is condensed.

A sample of the raw condensate is used to prepare the coating solution, the rest is put into water dissolved, and the chloride of the condensate is precipitated from this solution with hydrochloric acid, this separated and dried. (C 68.2%, N 8.296, atomic ratio C: N = 29.1: 3)

Example 92

For the synthesis of component B ₁ , no. 58, 1,4-Dlphenoxy-benzene prepared according to "Llebig's Annalen der Chemie", 350. p. 98 (1906) is bromomethylated analogously to Example 83 for 3 hours at 90 to 92 ° C and that Reaction product reacted with methanolic sodium hydroxide solution (OCHj: 19.2 pbw).

To produce the mixed condensate, 2.3 pbw. Dlazo-2, sulfate in 20 Vt. 86% phosphoric acid dissolved and 23Gt. Component Bi, No. 58, as a hot solution In 1 Vt. Glacial acetic acid registered. After 6 hours of condensation at 40 ° C and standing overnight, the raw condensate is used to prepare the coating solution.

The mixed condensate can be extracted from aqueous solution z. B. with HCI, methanesulfonic acid or benzenesulfonic acid fail.

Example 93

An intimate mixture of 10.8Gt. S-Methoxy-diphenylamln ^ -diazonlumchlorld (Diazo 2, chloride) (97.3%) and 0.96Gt. Paraformaldehyde is available in 11.8%. 93% long phosphoric acid stirred in. Then follow below good pipes 1,57Gt. 2,6-Bls- (methoxymethyl) -4-methyl-phenol (component Bi, no. 59). The mixture is then condensed under tubes for 24 hours at 40 ° C. A raw condensate is obtained which is clear in water Is soluble and does not lose this property even after months of storage at room temperature. 5 < >

However, if 2,6-B-methoxymethyl) -4-methyl-phenol is introduced into the phosphoric acid in the absence of dlazo compound and formaldehyde. so the product will dissolve quickly, but after a few seconds it will deposit Condensation product, which is very sparingly soluble in the acid and in hot water.

55 Example 94

32.3Gt. S-methoxy-dlphenyM-dlazonlum sulfate (Diazo 2, sulfate) are In 200Gl. 86% long phosphoric acid solved. With vigorous stirring, 8.5 pbw. molten diphenyl ether (component B, No. 60) added and then within 10 minutes In portions 3.0 Gt. Paraformaldehyde added. After IV, hourly condensation M at room temperature and 15 hours condensation at 40 ° C, the mixture is introduced into water, and the Fractions which are insoluble in water are separated off after the addition of cabbage. The aqueous solution is saturated with Saline solution filled the condensation product as chloride and again made up of water / saline solution fell over. Yield after drying in vacuo: 18.3% by weight. (C 54.2%, N 10.2 *; atomic ratio: 18.55: 3). The analysis suggests a molar ratio of dlazo compound: second component in the condensate of about 1: 0.4. The mean molecular weight determined as in Example 40 of the l-phenyl-3-methyl-pyrazolon- (5) Azo dye produced is 1611.

Example 95

32.3Gt. 3-Methoxy-dlphenylamine-4-dlazon! Umsulfat (Diazo 2, sulfate) are in 180Vt. 93S6Iger phosphoric acid dissolved. Separately, 17Gt. Dlphenylether (component B, No. 60) in 34%. Dissolved glacial acetic acid. The latter solution is poured with stirring together with 45 pbw. a 40%. aqueous formaldehyde solution into the solution of the diazo compound. The mixture is _{stirred for 6V for 2} hours without further supply of heat and then left to stand overnight. The very cloudy raw condensate is in 1000 Vt. Introduced water, extracted by shaking with ether and treated with enough charcoal that a clear filtrate is formed. The condensate is separated from the filtrate by adding tin chloride and common salt. Yield: 27% (C 47.5%, N 8.196; atomic ratio: 20.6: 3). This means that the mixed condensate has an excess of 7.6 gram atoms of carbon per mole of diazo compound.

The condensation products produced according to Betspiele 94 and 95 provide printing forms with good results Color acceptance if they are used in the catfish described in more detail in Examples 1 to 35.

¹⁵ Example 96

As in Example 40, a mixture of the following ingredients is condensed:

away)

5.5 Gt. 11.0 Gt. 51 Gt. 51 Gt. 5.2 Gt. 5.2 Gt.

86% tge phosphoric acid

4,4'-bis (methoxy / nethyl) -dlphenylether (component B ₁ , no. 41)

The clear raw condensates are a) In 290 Vt. or b) In 370 Vt. Stirring in methanol, the precipitates are with a) 80 Vt. or b) 3 χ per 100 Vt. Washed methanol and dried.

Yield: a) 8 pbw. (C 59.1%, N 6.116. P 5.6%; atomic ratio: 34: 3: 1.25)

b) 6.8 Gt. (C 63.5%, N 7.3%, P 3.3%; atomic ratio: 30.4: 3: 0.61)

The analysis result suggests a condensation ratio of diazo compound to second component of about 1: 1.5 (a) or 1: 1.24 (b).

35 Example 97

15.42Gt. Dlphenylamine-4-dlazonum sulfate (Diazo 1, sulfate) are sold in 100 Vt. 96.5% lger phosphoric acid dissolved and then 7.4Gt. Dimethyloloxamld (component Bi, No. 61) Sr added in small portions with stirring. It is condensed for 24 hours at room temperature. The condensation mixture is dissolved in 0.5 1 of water and ■ 40 then slowly with stirring at 40 ° C 80 Vt. 50% zinc chloride solution was added dropwise.

After cooling to + 10 ° C, the pleat is suctioned off, dissolved again in 0.5 l of water at 50 ° C, the precipitates Product again by adding dropwise Zlnkchlorld solution (45 Vt.) And isolating as described above. Yield: 16.3 Gt. According to the analysis, the condensation product contains 3 N atoms per 10.6 C atoms. (C 43.0%, N 14.2%). In the case of the diazo homocondensate, the C: N ratio would be 13: 3.

Example 98

30.9Gt. Dlphenylamine-4-dlazonium sulfate (Diazo 1, sulfate) (95%) and 14.4%. Adlplnsäuredlt ^ ild (component B, No. 62) are mixed and the mixture in 200 Vt. 90% longer methanesulfonic acid dissolved. Within 10 minutes are stirred for 6%. Paraformaldehyde and condense the mixture for 24 hours at room temperature. The raw condensate is in 75OVt. Dissolved water, likewise 25 Gt. Zinc chloride (anhydrous) dissolved, and the zinc chloride double salt of the condensation product is obtained by adding 10 pbv. Ethanol and 100 Vt. 36.5% hydrochloric acid precipitated. It is suctioned off, washed with 300 Vt. 2 η aqueous hydrochloric acid and dries at + 35 ° C. Yield: 45.2 pbw. According to the analysis, the condensation product contains about 0.5 mole of acid amd per mole of diazo compound.

Example 99

«> 15.42 Gt, Diphenylamine-4-dlazonlumuirat (Diazo 1, Sulphate) 05%) are in 100 Vt. Methanesulfonic acid (9096) dissolved. 10.8Gt. Finely powdered methylol-adlplnsäuredlamld (component B ₁ , No. 63) (94.7%) are In

Portions added while stirring well. When the spontaneous heating caused by the reaction

1 disappears, the mass is condensed for 25 hours at room temperature.

The raw condensate is in 500 Vt. Dissolved water. By adding 80 Vt. 50% longer Zlnkchlorld solution schel-

f'5 det the condensate as a sticky precipitate at room temperature. The mother liquor is decanted, the Filling in 500 Vt. Dissolve water at 50 "C and after cooling to +10" C again by adding 50 Vt. 50% longer Zlnkchlorld solution liked. The product is filtered off with suction and dried in vacuo. After the analysis the condensate contains about 0.7 molecules of Saurcamld per molecule of Dla / .ovcrblndung.

■ 58 '

Example 100

4.47Gt. Dlphenylamine-4-dlazonium phosphate (Diazo I, phosphate) (98.4%) are sold in 60 Vt. 92% phosphoric acid dissolved. Then 4.85 Gt. Trimethylolcltramide (component B ₁ , no. 64) (86.3%, remainder water) was added and the mass was condensed for 45 hours at room temperature. The condensation mixture, which is clearly soluble in water, is charged at 30 pbv. Diluted methanol and the mixture in 500 Vt. Stir in isopropanol. The reaction product which separates out is filtered off with suction and dried in vacuo. Yield: 10.8 pbw. According to the analysis, the ratio N: C = 3: 10.8 (C 28.8%, N 9.3%)

Examples 101 and 102

These examples show how two other diazo compounds (No. 13 and! 4) with a component Bi in an acidic condensation medium to form mixed condensates can be condensed.

In both examples, the diazo compounds are in the condensation medium in the form of their metal halide double salts solved. Dry air is passed through the mixture until there is no more hydrogen chloride escapes. Then the second component is added and the condensation at room temperature for the specified Periods carried out. Mixed condensals are formed which are clearly soluble in water.

If component B _{(is introduced} alone into the condensation medium, a homocondensate of component B is formed during a condensation process of the same duration, which separates easily from the condensation agent and does not dissolve when water is added.

The following table shows the quantities used and the duration of the condensation process: Example 101 Example 102

Condensation medium
Diazo compound

Second component Methunsulfonic acid (10 percent) 90% methanesulfonic acid y \ 0 percent)

2.5-Dimethoxy-4- (N-methyl-N-phenylmercaptoacetylamino) -benzenediazonium chloride + ¹ A mol zinc chloride (N 8.8%) (0.95% by weight)

1,4-bis-hydroxymethylbenzene (0.1% by weight) (component B ₍ , No. 38)

Duration of the 4 hour condensation process:

4- | N-methyl-N - (/? - phenylmercaptoethyl) -aminoj-ben7.oldiazoniumchlorid
+ '/ j MoI tin tetrachloride
(N 6.3%) (1.33 Gt.)

1,4-bis-hydroxymethylbenzene
(0.14 parts) (component B ,, No. 38)

4 hours

Examples 103-108

In each of the following examples, 0.74Gt. Dlphenylamine-4-dlazonum sulphate (Diazo Ά, sulphate) (2.5 millimoles) Dissolved in as much 90% long methanesulphonic acid as required to form 5 percent. Solution is needed. The corresponding second component (2.5 Mllllmol) is 0.5 Vt. a 30% aqueous formaldehyde solution, the mixture is heated on a steam bath for a few seconds and then dissolved in as little organic solvent as possible with heating.

Then half of the solution of the Zwell component is added to the diazo solution prepared first (Test series a) stirred in. The other half of the solution of the second component is 5 Vt. 90% long methanesulfonic acid (Test series b - comparative test) added. After about 20 minutes standing, the Reaction mixtures are first assessed for their appearance and then processed further.

Solutions of component B (second components) example

103

104

106

107

108

p-Toluene sulfonic acid anilide
(Component B, No. 65, Table 1)

p-Toluolsulfonsäureäthylamid
(Component B, No. 66, Table I)

1,3-benzene disulfonic acid diumide
(Component B, No. 67, Table 1)

PhenylthiourestolT
(Component B, No. 68, Table I)

Phenylurestol T.
(Component B, No. 69, Table 1)

0.62 Gt. -

0.5 gl. -

0.59 Gt. -

0.38 Gl. -

0.34 Gt.

59

continuation

example

103

104

105

106

107

2-Benzoylamino-1,4-diethoxybenzoI (Component B, No. 70, Table 1)

30% aqueous formaldehyde solution

Methanol

Glacial acetic acid

108

- - 0.68Gt.

0.5 Vt. 0.5 Vl. 0.5 Vt. 0.5 Vt. 0.5 Vt. 0.5 Vl.

1.8 Vt. 0.9 Vt. - 1.6 Vt. 1.1 Vt. -

2.0Vt. - - 2.0Vt.

Assessment of the appearance of the condensation games

example

! 03

106

107

108

Test series a

clear after 3 hours

clear after 20 hours

diluted with water, strong yellow slightly cloudy to tenfold precipitation of the original
lot

Test series b
After 3 hours

after 20 hours

strong clear

Precipitation

strong clear

Precipitation

• hi dilute; strong oily with water

to 10 times precipitation precipitation the original

lot

races clear
(first
very cloudy clear clear clear clear clear clear clear very cloudy clear very cloudy slightly cloudy

thickness
flaky
Precipitation clear clear clear thickness
flaky
Precipitation clear clear clear thickness
flaky
Precipitation clear,
but will
after a long time
Stand cloudy flaky
Precipitation thickness
Precipitation

The condensation mixtures άςτ test series b) are diluted with water and then freed from precipitation and turbidity by adding a little charcoal and suction. Clear solutions are thus obtained which do not produce any precipitations when a saturated NaCl solution or a zinc chloride solution is added.

The solutions obtained according to test series a) (Examples 104 to 108) are, if necessary, with charcoal clarified (Examples 104, 105, 107 and 108) and then mixed with saturated saline and zinc chloride. The precipitating metal halide double salts of the condensates are separated off, dried and analyzed.

The precipitate produced according to Example 103 is dissolved in warm water, again by adding hydrochloric acid precipitated, separated, dried and analyzed in this form.

The following analysis results in connection with the above results of the assessment the appearance suggest that mixed condensates were formed. In addition, the analysis result appears In some cases, on a certain degree of change of the second component during the condensation to point out.

Aruilysis events 103 104 HlS 106 107 108 example 60.2 "i,
9.8 "■;<
3.47 · '... 41.0 "/ o
9.7%
5, often »··« 33.7%
X, 6%
4.31% 42.2 '■: ·
12.4%
6.11% 27.1%
6.9 "/ (i
3.16% 39.5%
7.8% C.
N
ND

continuation

example 40.2 18.9 103 18.3 104 105 106 107 108 17.7 Atomic ratio 5.65 3.83 4.0 3.0 C. 2.0 2.0 2.0 16.2 20.0 - N example 4.06 4.36 ND 2.0 2.0 109

15.5Gt. Dlphenylamine-4-dlazonum sulphate (Diazo 1, sulphate) are in 100 Vt. 80% long sulfuric acid dissolved. A mixture of 6.9% is poured into this solution under pipes. 2-phenoxy-ethanol (component B, no. 18), 14.8 Gt. a 50% lgen aqueous glyoxylic acid solution and 2 Vt. Glacial acetic acid, which makes the temperature inside short tent rises to 58 ° C. It is lowered to 40 ° C. within 4 minutes by cooling. Then the mixture is cooled to room temperature, stirred for 5 hours at this temperature and then left overnight stand. A clear condensation mixture results. After adding 350 Vl. Water becomes a condensation product precipitated, which is suctioned off, carefully washed with water and dried. You get 21.1 Gt. a greenish brown powder that is almost insoluble in aqueous solutions and organic solvents Is. (C 56.0 «, N 7.0%; atomic ratio: 28: 3)

Since one by condensation of phenoxyethanol with glyoxylic acid under the specified conditions Condensate is obtained with relatively good water solubility, which precipitates as a polyacid on diazonium salts works. It is not ruled out that the isolated product also contains such a precipitate.

6Γ

Claims (11)

Patent claims: 1. Photosensitive condensation product containing Dlazonlumgnippen, consisting of recurring Units of diazonium salts of the general formula (R'-R'-yi'-NjX or of carbazole-3-dIazo- nium salt, S-methoxy-dlphenylenoxId-1-dlazonum salt or 2,5-dimethoxy-4 - [(N-methyl-N-phenylmercaptoacetyl) -amino] benzodiazonum salt and compounds B in an average molar ratio of about 1: 0.1 to 1:20, connected by twelve intermediate links derived from an active carbonyl compound are obtainable by reacting 2,5-di-methoxy-4- | [(N-methyl-N-phenyImercapto-acetyl) -amino] benzene diazonium salt, Carbazole-3-diazonium salt, 3-methoxy-diphenyioxide-2-diazonium salt or a diazonium ίο salt <ler general formula (R'-R ^J -) ,,; R ² -NiX, wherein X is the anion of the dlazonium compound, ρ an integer from 1 to 3, R ^{1 is} an aromatic radical with at least one suitable for condensation with an active carbonyl compound deleted position, such as an unsubstituted or by one or more alkyl or alkoxy groups substituted phenyl radical, R ^{1 is} an optionally substituted phenylene group, R ^{3 is} a single bond or one of the groups: 20 V -CMCHiI-NR ⁴ -. -S- (CH ₂ ), - NR ⁴ -, -OR ^s -O-, -O-,
25 -S- or -CO-NR ⁴ -, wherein 30 q is a number from 0 to 5, r is a number from 2 to S. R ^{4 is} hydrogen, an alkyl group with 1 to 5 carbon atoms, an aralkyl group with 7 to 12 carbon atoms or an aryl group with 6 to 12 carbon atoms and « ^{5 is} an arylene group with 6 to 12 carbon atoms, in a strongly acidic medium with an active carbonyl compound and a compound B, which is an aromatic AmIn, a phenol, thlophenol, phenol ether, aromatic ThloSther, aromatic hydrocarbon, is an aromatic heterocyclic compound or an organic acid amide, each of these compounds B is free from Dlazonlumgruppen and at least one for condensation with active Carbonylverbln- • »o qualified position. 2. Condensation product according to claim 1, obtainable by reacting diazonium salts of the general formula are derived where R ^1o , R ″ and R ^{12 are} hydrogen, halogen, alkyl groups with 1 to 3 carbon atoms or alkoxy groups with I to S mean carbon atoms, and X is the anion of the dlazonium salt. <· < 3. Condensation product according to claim I, obtainable by reacting S-Methoxydlphenylamln ^ -di azoneum salt. 4. Condensation product according to claim I, obtainable by reacting with formaldehyde as the active one Carbonyl compound. 5. Condensation product according to claim I, obtainable by reaction with Dlphenyläther or Dlphenylsulfld as connection B. 6. A process for the preparation of condensation products containing dlazonium groups according to claim 1, characterized in that a 2,5-Dlmethoxy-4 - [(N-methyl-N-phenylmercapto-acelyl) -amino] benzomlazonium salt, carbazole-3-diazonium salt, 3 Methoxy-dlphenylenoxld-2-dlazonum salt or a s dlazonum salt of the general formula (R'-R ³ -) _p R ² -NiX, in which R ¹ , R ² , R ¹ , X and ρ have the meaning given in claim 1. Reacts in a strongly acidic medium at a temperature not above about 7C C with an active carbonyl compound and an aromatic amine, a phenol, thiophenol, phenol ether, an aromatic thloether, aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amd, each of the latter compounds Is free of diazonium groups and has at least one position capable of condensation with an active carbonyl compound. 7. The method according to claim 6, characterized in that the condensation medium is phosphoric acid, Methanesulfonic acid or sulfuric acid is used in a concentration of about 70 to 100%. 8. The method according to claim 7, characterized in that the condensation medium 80 to 100ase orthophosphoric acid is used. 9. The method according to claim 6, characterized in that the condensation in the temperature range from about 10 to 50 ° C. 10. The method according to claim 6, characterized in that formaldehyde is used as the active carbonyl compound. ²ⁿ 11. Avoidance of a condensation product according to claim 1 as a light-sensitive compound In light